CN115096873A - Method for detecting mercury element in water body and nano-alloy modified filter paper - Google Patents
Method for detecting mercury element in water body and nano-alloy modified filter paper Download PDFInfo
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- G—PHYSICS
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- 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
- G01N21/71—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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- B01D39/00—Filtering material for liquid or gaseous fluids
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- G—PHYSICS
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Abstract
The invention provides a detection method of mercury elements in a water body and nano-alloy modified filter paper, and relates to the technical field of environmental monitoring, wherein the detection method comprises the following steps: soaking the nano alloy modified filter paper in a mercury-containing solution to be detected for a first preset time period, and then taking out the filter paper to obtain first filter paper adsorbed with mercury ions; performing mercury element detection on the first filter paper based on a laser-induced breakdown spectroscopy (LIBS) technology to obtain a first spectrum signal corresponding to the mercury-containing solution to be detected; and determining the mercury concentration of the mercury-containing solution to be detected based on the first spectrum signal and a calibration curve, wherein the calibration curve is used for reflecting the corresponding relation between the mercury concentration and the spectrum signal intensity. The invention realizes the enrichment of mercury elements in the water body by modifying the filter paper based on the nano alloy, and realizes the rapid in-situ detection of the mercury elements in the water body by combining the laser-induced breakdown spectroscopy technology, thereby not only having low detection cost and high sensitivity, but also having simple operation.
Description
Technical Field
The invention relates to the technical field of environmental monitoring, in particular to a method for detecting mercury elements in a water body and nano-alloy modified filter paper.
Background
Mercury (Hg) in water is used as a highly toxic pollutant, has a strong biological accumulation effect, and seriously harms the balance of an ecological system and the health of a human body. In industrial production, the waste water with excessive mercury is discharged to the natural environment, which poses great threat to aquatic organisms and human health. Therefore, the rapid in-situ detection of the mercury element in the water body is very important.
In the related art, the mercury element in the water body is usually detected by adopting an atomic absorption spectrometry, an atomic fluorescence spectrometry, a plasma mass spectrometry and the like, and although the methods have high detection sensitivity, the methods are complex to operate, usually require complex pretreatment, are usually only suitable for laboratory detection, and are difficult to realize the rapid in-situ detection of the mercury element in the water body.
Laser-induced breakdown spectroscopy (LIBS) is an in-situ, rapid, and remotely analyzable elemental spectroscopy (el bs) technique that mainly uses pulsed Laser to ablate a sample to generate plasma and emit a specific spectral signal, and realizes qualitative and quantitative analysis of elements in the sample by analyzing the specific spectral signal. However, in the process of detecting the mercury element, the LIBS technology is difficult to realize high-sensitivity detection of the mercury element due to the low content of the mercury element in the water body.
At present, the following two methods for detecting mercury elements based on the LIBS technology are mainly available: (1) the method for detecting mercury elements based on the electrolytic method for pre-concentrating mercury ions in water and combining the LIBS technology is complex to operate and high in electrode enrichment cost; (2) the method for enriching mercury in water by using the shear thickening liquid and detecting mercury elements by using the LIBS technology is complex in mercury ion enrichment and difficult to apply to actual detection. Therefore, how to realize the rapid and high-sensitivity in-situ detection of the mercury element in the water body under the conditions of ensuring low detection cost and simple operation becomes an urgent problem to be solved in the industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for detecting mercury elements in a water body and nano-alloy modified filter paper.
In a first aspect, the present invention provides a method for detecting mercury elements in a water body, including:
soaking the nano-alloy modified filter paper in a mercury-containing solution to be detected for a first preset time period, and then taking out the filter paper to obtain first filter paper adsorbed with mercury ions;
performing mercury element detection on the first filter paper based on a laser-induced breakdown spectroscopy (LIBS) technology to obtain a first spectrum signal corresponding to the mercury-containing solution to be detected;
and determining the mercury concentration of the mercury-containing solution to be detected based on the first spectrum signal and a calibration curve, wherein the calibration curve is used for reflecting the corresponding relation between the mercury concentration and the spectrum signal intensity.
Optionally, according to the method for detecting mercury elements in a water body provided by the invention, the nano-alloy modified filter paper is gold-silver nano-alloy modified filter paper;
the gold-silver nano alloy modified filter paper is prepared by the following steps:
mixing a silver nitrate solution and a tetrachloroauric acid solution to obtain a first mixed solution;
soaking a piece of common filter paper in the first mixed solution for a second preset time, and then taking out the common filter paper to obtain second filter paper;
and soaking the second filter paper in a sodium borohydride solution for a third preset time, and taking out to obtain the gold-silver nano alloy modified filter paper.
Optionally, according to the method for detecting mercury elements in a water body provided by the invention, the nano-alloy modified filter paper is silver-palladium nano-alloy modified filter paper;
the filter paper modified by the silver-palladium nano alloy is prepared by the following steps:
mixing a silver nitrate solution with a sodium tetrachloropalladate solution to obtain a second mixed solution;
soaking a piece of common filter paper in the second mixed solution for a fourth preset time, and taking out to obtain a third filter paper;
and soaking the third filter paper in a sodium borohydride solution for a fifth preset time, and taking out to obtain the silver-palladium nano alloy modified filter paper.
Optionally, according to the method for detecting mercury elements in a water body provided by the invention, the nano-alloy modified filter paper is silver-platinum nano-alloy modified filter paper;
the silver-platinum nano alloy modified filter paper is prepared by the following steps:
mixing the silver nitrate solution with the potassium tetrachloroplatinate solution to obtain a third mixed solution;
soaking a piece of common filter paper in the third mixed solution for a sixth preset time, and taking out to obtain a fourth filter paper;
and soaking the fourth filter paper in a sodium borohydride solution for a seventh preset time, and taking out the fourth filter paper to obtain the silver-palladium nano-alloy modified filter paper.
Optionally, before determining the mercury concentration of the mercury-containing solution to be detected based on the first spectrum signal and the calibration curve, the method for detecting mercury element in a water body according to the present invention further includes:
preparing mercury ion solutions with different concentrations;
respectively soaking a plurality of pieces of nano-alloy modified filter paper in the mercury ion solutions with different concentrations for an eighth preset time period, and then taking out the filter paper to obtain a plurality of pieces of fifth filter paper adsorbed with mercury ions;
respectively detecting mercury elements in the fifth filter paper based on the LIBS technology to obtain second spectrum signals respectively corresponding to the mercury ion solutions with different concentrations;
and fitting the calibration curve based on a plurality of second spectrum signals and the concentration of the mercury ion solution corresponding to each second spectrum signal.
Optionally, according to the method for detecting mercury elements in a water body provided by the present invention, fitting the calibration curve based on a plurality of second spectrum signals and the concentration of the mercury ion solution corresponding to each of the second spectrum signals includes:
determining the intensity of the first target spectral signal at the wavelength to which the elemental mercury is characteristically sensitive in each of the second spectral signals;
and fitting the calibration curve based on the intensity of all the first target spectral signals and the concentration of the mercury ion solution corresponding to each second spectral signal.
Optionally, according to the method for detecting mercury element in a water body provided by the present invention, determining the mercury concentration of the mercury-containing solution to be detected based on the first spectrum signal and the calibration curve includes:
determining the intensity of a second target spectral signal at a wavelength to which the elemental mercury is characteristically sensitive in the first spectral signal;
matching the intensity of the second target spectrum signal by using the calibration curve, and determining a target point in the calibration curve, wherein the absolute difference between the intensity of the spectrum signal corresponding to the target point and the intensity of the second target spectrum signal is the minimum;
and determining the mercury concentration corresponding to the target point as the mercury concentration of the mercury-containing solution to be detected.
In a second aspect, the present invention provides a nano-alloy modified filter paper applied to the method for detecting mercury in a water body in the first aspect, including:
the gold and silver nanoparticle composite paper comprises first substrate filter paper and gold and silver nanoparticles modified on the first substrate filter paper;
the gold and silver nanoparticles are 40 nm-50 nm in size, and contain gold elements and silver elements in equal proportion.
In a third aspect, the present invention provides a nano-alloy modified filter paper applied to the method for detecting mercury element in a water body in the first aspect, comprising:
a second substrate filter paper and silver palladium nanoparticles decorated on the second substrate filter paper;
the size of the silver palladium nano particles is 40 nm-50 nm, and the silver palladium nano particles contain silver elements and palladium elements in equal proportion.
In a fourth aspect, the present invention provides a nano-alloy modified filter paper applied to the method for detecting mercury element in a water body in the first aspect, including:
a third substrate filter paper and silver platinum nanoparticles decorated on the third substrate filter paper;
wherein the silver platinum nanoparticles have a size of 40 nm to 50 nm; the silver-platinum nano particles contain silver element and platinum element in equal proportion.
According to the method for detecting the mercury element in the water body, the mercury element enrichment in the water body is realized through the filter paper modified based on the nano alloy, and the rapid in-situ detection of the mercury element in the water body is realized by combining the laser-induced breakdown spectroscopy technology, so that the detection cost is low, the sensitivity is high, and the operation is simple.
Drawings
In order to more clearly illustrate the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic flow chart of a method for detecting elemental mercury in a water body according to the present invention;
FIG. 2 is a schematic diagram of the nano-alloy modified filter paper provided by the invention for adsorbing mercury ions in a water body;
FIG. 3 is a schematic structural diagram of an LIBS detection apparatus provided in the present invention;
FIG. 4 is a schematic diagram showing LIBS spectrum comparison of the silver nanoparticle modified filter paper and the gold-silver nano-alloy modified filter paper provided by the invention with the LIBS technology to realize mercury element detection;
FIG. 5 is a schematic spectrum diagram of the detection of mercury solutions with different concentrations by combining gold-silver nano-alloy modified filter paper with LIBS technology.
Reference numerals:
201: nano-alloy modified filter paper; 202: mercury ion solution to be detected; 203: centrifuging the tube; 204: a glass slide; 301: a spectrum collection head; 302: an optical fiber; 303: a spectrometer; 304: a timing signal transmission line; 305: a signal transmission line; 306: a laser mirror; 307: a laser; 308: a laser focusing mirror; 309: filter paper adsorbing mercury ions; 310: glass slide; 311: a displacement platform; 312: and (4) a computer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The method for detecting mercury in a water body provided by the invention is described below with reference to fig. 1 to 5.
Fig. 1 is a schematic flow chart of a method for detecting mercury in a water body provided by the present invention, and as shown in fig. 1, the method includes:
and 120, determining the mercury concentration of the mercury-containing solution to be detected based on the first spectrum signal and a calibration curve, wherein the calibration curve is used for reflecting the corresponding relation between the mercury concentration and the spectrum signal intensity.
Specifically, in order to overcome the defect that the existing mercury element detection method is difficult to ensure that the rapid and high-sensitivity in-situ detection of the mercury element in the water body is realized under the conditions of low detection cost and simple operation, the invention realizes the mercury element enrichment in the water body by modifying filter paper based on nano alloy and realizes the rapid in-situ detection of the mercury element in the water body by combining a laser-induced breakdown spectroscopy technology, so that the detection cost is low, the sensitivity is high, and the operation is simple.
Optionally, the filter paper modified by the nano alloy may be taken out after being soaked in the mercury-containing solution to be detected for a first preset time period, so as to obtain the first filter paper adsorbed with the mercury ions.
Optionally, after the nano-alloy modified filter paper is soaked in the mercury-containing solution to be detected, the filter paper may be taken out after the mercury-containing solution to be detected is oscillated on the oscillator for a first preset time period, so as to obtain the first filter paper adsorbed with mercury ions.
Alternatively, the first preset time period may be adaptively set according to practical applications, for example, the first preset time period may be 2 minutes, 5 minutes, or 10 minutes, and the like, which is not particularly limited in the present invention.
Optionally, mercury element detection may be performed on the first filter paper based on a laser-induced breakdown spectroscopy LIBS technique, so as to obtain a first spectrum signal corresponding to the mercury-containing solution to be detected.
It can be understood that the filter paper modified by the nano alloy is used as the mercury element carrier, so that the problems of plasma quenching and the like when the LIBS directly detects the mercury element in the solution can be avoided, and the rapid and efficient detection of the mercury element can be realized more conveniently.
Optionally, the mercury concentration of the mercury-containing solution to be measured may be determined based on the first spectral signal and a calibration curve, wherein the calibration curve is used for reflecting a corresponding relationship between the mercury concentration and the intensity of the spectral signal.
According to the method for detecting the mercury element in the water body, the mercury element in the water body is enriched by modifying the filter paper based on the nano alloy, and the rapid in-situ detection of the mercury element in the water body is realized by combining the laser-induced breakdown spectroscopy technology, so that the detection cost is low, the sensitivity is high, and the operation is simple.
Optionally, the nano-alloy modified filter paper is gold-silver nano-alloy modified filter paper;
the gold-silver nano-alloy modified filter paper is prepared by the following steps:
mixing silver nitrate (AgNO) 3 ) Solution with tetrachloroauric acid (HAuCl) 4 ) Mixing the solutions to obtain a first mixed solution;
soaking a piece of common filter paper in the first mixed solution for a second preset time, and then taking out the common filter paper to obtain second filter paper;
and soaking the second filter paper in a sodium borohydride solution for a third preset time, and taking out to obtain the gold-silver nano alloy modified filter paper.
Specifically, the preparation of the gold-silver nano-alloy modified filter paper can comprise the following steps 1.1-1.3:
step 1.1, mixing a silver nitrate solution and a tetrachloroauric acid solution to obtain a first mixed solution.
Alternatively, the first mixed solution may be prepared by mixing a silver nitrate solution and a tetrachloroauric acid solution in an equal ratio.
And step 1.2, soaking a piece of common filter paper in the first mixed solution for a second preset time, and then taking out the common filter paper to obtain a second filter paper.
Alternatively, the second preset time period may be adaptively set according to practical applications, for example, the second preset time period may be 1 minute, 2 minutes, or 5 minutes, and the like, which is not particularly limited in the present invention.
Alternatively, a filter paper with the size of 10 mm × 10 mm may be soaked in the first mixed solution, then the first mixed solution is placed on an oscillator to be oscillated for 2 minutes, then the filter paper is taken out, and the filter paper is washed once by using absolute ethyl alcohol and deionized water respectively to remove the excess AgNO on the surface of the filter paper 3 And HAuCl 4 。
Step 1.3, soak the second filter paper in sodium borohydride (NaBH) 4 ) And taking out the solution after the third preset time to obtain the gold-silver nano-alloy modified filter paper.
Optionally, the third preset time period may be adaptively set according to the actual application, for example, the third preset time period may be 1 minute, 2 minutes, or 5 minutes, and the invention is not limited in this regard.
Optionally, the second filter paper may be soaked in a sodium borohydride solution, and placed on an oscillator to oscillate for 1 minute to allow sufficient reaction, and then the treated filter paper is taken out and washed with deionized water for 1 to 2 times, so as to finally obtain the filter paper modified with gold (Au) silver (Ag) nano alloy.
It can be understood that the filter paper modified by the gold-silver nano alloy can realize the high-efficiency adsorption of mercury elements in the water body, and compared with the filter paper modified by single gold or silver nano particles, the filter paper modified by the gold-silver nano alloy has the advantage that the adsorption effect can be greatly improved.
Optionally, the nano-alloy modified filter paper is silver-palladium nano-alloy modified filter paper;
the filter paper modified by the silver-palladium nano alloy is prepared by the following steps:
mixing a silver nitrate solution with a sodium tetrachloropalladate solution to obtain a second mixed solution;
soaking a piece of common filter paper in the second mixed solution for a fourth preset time, and taking out to obtain a third filter paper;
and soaking the third filter paper in a sodium borohydride solution for a fifth preset time, and taking out to obtain the silver-palladium nano alloy modified filter paper.
Specifically, the preparation of the silver palladium nano alloy modified filter paper can comprise the following steps 2.1-2.3:
and 2.1, mixing the silver nitrate solution with the sodium tetrachloropalladate solution to obtain a second mixed solution.
Alternatively, the silver nitrate solution and the sodium tetrachloropalladate solution may be mixed in equal proportion to prepare a second mixed solution.
And 2.2, soaking a piece of common filter paper in the second mixed solution for a fourth preset time, and taking out to obtain a third piece of filter paper.
Optionally, the fourth preset time period may be adaptively set according to practical applications, for example, the fourth preset time period may be 1 minute, 2 minutes, or 5 minutes, and the like, which is not particularly limited in the present invention.
Alternatively, filter paper with the size of 10 mm × 10 mm may be soaked in the second mixed solution, then the second mixed solution is placed on an oscillator to oscillate for 2 minutes, and then the filter paper is taken out, and the filter paper is washed once by using absolute ethyl alcohol and deionized water respectively, so as to remove the redundant silver nitrate solution and sodium tetrachloropalladate solution on the surface of the filter paper.
And 2.3, soaking the third filter paper in a sodium borohydride solution for a fifth preset time, and taking out to obtain the silver-palladium nano alloy modified filter paper.
Optionally, the fifth preset time period may be adaptively set according to practical applications, for example, the fifth preset time period may be 1 minute, 2 minutes, or 5 minutes, and the like, which is not specifically limited in the present invention.
Optionally, the third filter paper may be soaked in a sodium borohydride solution, and placed on an oscillator to oscillate for 1 minute to allow sufficient reaction, and then the treated filter paper is taken out and washed with deionized water for 1 to 2 times, so as to finally obtain the filter paper modified with the silver (Ag) palladium (Pd) nano alloy.
It can be understood that the filter paper modified by the silver palladium nano alloy can realize high-efficiency adsorption of mercury elements in the water body, and compared with the filter paper modified by single silver or palladium nano particles, the filter paper modified by the silver palladium nano alloy has the advantage that the adsorption effect can be greatly improved.
Optionally, the nano-alloy modified filter paper is silver-platinum nano-alloy modified filter paper;
the silver-platinum nano-alloy modified filter paper is prepared by the following steps:
mixing the silver nitrate solution with the potassium tetrachloroplatinate solution to obtain a third mixed solution;
soaking a piece of common filter paper in the third mixed solution for a sixth preset time, and taking out to obtain a fourth filter paper;
and soaking the fourth filter paper in a sodium borohydride solution for a seventh preset time, and taking out the fourth filter paper to obtain the silver-palladium nano-alloy modified filter paper.
Specifically, the preparation of the silver-platinum nano-alloy modified filter paper can comprise the following steps 3.1-3.3:
and 3.1, mixing the silver nitrate solution with the potassium tetrachloroplatinate solution to obtain a third mixed solution.
Alternatively, the third mixed solution may be prepared by mixing the silver nitrate solution and the potassium tetrachloroplatinate solution in an equal ratio.
And 3.2, soaking a piece of common filter paper in the third mixed solution for a sixth preset time, and then taking out to obtain a fourth filter paper.
Optionally, the sixth preset time period may be adaptively set according to practical applications, for example, the sixth preset time period may be 1 minute, 2 minutes, or 5 minutes, and the present invention is not limited in this respect.
Alternatively, a filter paper with a size of 10 mm × 10 mm may be soaked in the third mixed solution, then the third mixed solution is placed on an oscillator to oscillate for 2 minutes, and then the filter paper is taken out, and the filter paper is washed once with absolute ethyl alcohol and deionized water respectively, so as to remove the excess silver nitrate solution and potassium tetrachloroplatinate solution on the surface of the filter paper.
And 3.3, soaking the fourth filter paper in a sodium borohydride solution for a seventh preset time, and taking out the fourth filter paper to obtain the silver-palladium nano alloy modified filter paper.
Optionally, the seventh preset time period may be adaptively set according to practical applications, for example, the seventh preset time period may be 1 minute, 2 minutes, or 5 minutes, and the like, which is not specifically limited in the present invention.
Optionally, the fourth filter paper may be soaked in a sodium borohydride solution, and placed on an oscillator to oscillate for 1 minute to allow sufficient reaction, and then the treated filter paper is taken out and washed with deionized water for 1 to 2 times, so as to obtain the filter paper modified with silver (Ag) platinum (Pt) nano-alloy.
It can be understood that the filter paper modified by the silver-platinum nano alloy can realize the high-efficiency adsorption of mercury elements in the water body, and compared with the filter paper modified by single silver or platinum nano particles, the adsorption effect can be greatly improved.
Specifically, in the embodiment of the present invention, the adopted nano-alloy modified filter paper may include, but is not limited to, a gold-silver nano-alloy modified filter paper, a silver-palladium nano-alloy modified filter paper, and a silver-platinum nano-alloy modified filter paper, that is, the gold-silver nano-alloy modified filter paper may be used as an mercury element carrier, or the silver-palladium nano-alloy modified filter paper may be used as an mercury element carrier, or the silver-platinum nano-alloy modified filter paper may be used as an mercury element carrier, or the nano-alloy modified filter paper of other precious metals may be used as an mercury element carrier, which is not specifically limited in the present invention.
It can be understood that in the embodiment of the present invention, mercury ions in the water body are enriched by utilizing the amalgam reaction between precious metals such as gold and silver and mercury elements; by modifying the nanoparticles such as gold and silver on the surface of the filter paper, detection based on the LIBS technology can be better facilitated on one hand, and on the other hand, the nanoparticles such as gold and silver have larger specific surface area and can be combined with more mercury elements, so that the enrichment amount of the mercury elements is greatly improved.
Optionally, before determining the mercury concentration of the mercury-containing solution to be detected based on the first spectrum signal and the calibration curve, the method further includes:
preparing mercury ion solutions with different concentrations;
respectively soaking a plurality of pieces of nano alloy modified filter paper in the mercury ion solutions with different concentrations for an eighth preset time period, and taking out the filter paper to obtain a plurality of pieces of fifth filter paper adsorbed with mercury ions;
respectively detecting mercury elements in the fifth filter paper based on the LIBS technology to obtain second spectrum signals respectively corresponding to the mercury ion solutions with different concentrations;
and fitting the calibration curve based on a plurality of second spectrum signals and the concentration of the mercury ion solution corresponding to each second spectrum signal.
Specifically, in the embodiment of the present invention, the calibration curve may be determined by the following method, including step 4.1 to step 4.4:
and 4.1, preparing mercury ion solutions with different concentrations.
For example, 5 mL of mercury ion solutions of different concentrations (e.g., 0 ppm, 0.1 ppm, 1 ppm) can be prepared.
And 4.2, respectively soaking the multiple pieces of nano-alloy modified filter paper in mercury ion solutions with different concentrations for an eighth preset time period, and then taking out the multiple pieces of nano-alloy modified filter paper to obtain multiple pieces of fifth filter paper adsorbed with mercury ions.
Optionally, the eighth preset time period may be adaptively set according to practical applications, for example, the eighth preset time period may be 5 minutes, 8 minutes, or 10 minutes, and the like, which is not specifically limited in the present invention.
For example, a plurality of pieces of gold-silver nano-alloy modified filter paper sheets can be respectively soaked in mercury ion solutions with different concentrations, and the mercury ion solutions can be taken out after being placed on an oscillator and oscillated for 10 minutes.
And 4.3, respectively carrying out mercury element detection on the fifth filter paper based on an LIBS technology, and obtaining second spectrum signals respectively corresponding to mercury ion solutions with different concentrations.
And 4.4, fitting a calibration curve based on the plurality of second spectrum signals and the concentration of the mercury ion solution corresponding to each second spectrum signal, wherein the calibration curve can reflect the corresponding relation between the concentration of the mercury ions and the intensity of the spectrum signals.
Optionally, fitting the calibration curve based on a plurality of second spectral signals and the concentration of the mercury ion solution corresponding to each of the second spectral signals includes:
determining the intensity of the first target spectral signal at the wavelength to which the elemental mercury is characteristically sensitive in each of the second spectral signals;
and fitting the calibration curve based on the intensity of all the first target spectral signals and the concentration of the mercury ion solution corresponding to each second spectral signal.
Specifically, after the second spectrum signals are obtained, the intensities of the first target spectrum signals at the characteristic sensitive wavelengths of the mercury elements in the second spectrum signals can be determined, and a calibration curve is further fitted based on the intensities of all the first target spectrum signals and the concentration of the mercury ion solution corresponding to each second spectrum signal.
Optionally, the characteristic sensitivity wavelength of the mercury element is 253.7 nm.
Optionally, the spectral intensity corresponding to the spectral signal with the wavelength of 253.7 nm in the second spectral signal can be determined as the intensity of the first target spectral signal.
Optionally, determining the mercury concentration of the mercury-containing solution to be detected based on the first spectrum signal and the calibration curve includes:
determining the intensity of a second target spectral signal at a wavelength to which the elemental mercury is characteristic of in the first spectral signal;
matching the intensity of the second target spectrum signal by using the calibration curve, and determining a target point in the calibration curve, wherein the absolute difference between the intensity of the spectrum signal corresponding to the target point and the intensity of the second target spectrum signal is the minimum;
and determining the mercury concentration corresponding to the target point as the mercury concentration of the mercury-containing solution to be detected.
Specifically, the intensity of the second target spectral signal at the characteristic sensitive wavelength of the mercury element in the first spectral signal may be determined, and then the intensity of the second target spectral signal is matched by using a calibration curve to determine a target point in the calibration curve, where an absolute difference between the intensity of the spectral signal corresponding to the target point and the intensity of the second target spectral signal is the minimum, and then the mercury concentration corresponding to the target point is further determined to be the mercury concentration of the mercury-containing solution to be detected.
Optionally, the spectral intensity corresponding to the spectral signal with the wavelength of 253.7 nm in the first spectral signal can be determined as the intensity of the second target spectral signal.
Fig. 2 is a schematic diagram of the nano alloy modified filter paper provided by the present invention for adsorbing mercury ions in a water body, as shown in fig. 2, the nano alloy modified filter paper 201 is placed in a centrifuge tube 203 filled with a liquid to be tested 202 for mercury ions, and is oscillated for 10 minutes in an oscillator, the filter paper after adsorbing mercury ions is taken out to be naturally air-dried and then is adhered on a glass slide 204, and the glass slide adhered with the filter paper for testing mercury ions is placed on a three-dimensional displacement platform for testing.
Alternatively, the preparation process of the nano-alloy modified filter paper may include: placing filter paper with uniform size in a centrifuge tube filled with a mixed solution of silver nitrate and tetrachloroauric acid, oscillating for 2 minutes in an oscillator, taking out the filter paper, washing the filter paper once with absolute ethyl alcohol and deionized water respectively, placing the washed filter paper in the centrifuge tube filled with a sodium borohydride solution, oscillating for 1 minute in the oscillator, washing the filter paper for 1-2 times with the deionized water after taking out the filter paper, and obtaining the filter paper with the surface modified with Au and Ag nano alloy, namely the gold and silver nano alloy modified filter paper.
Alternatively, in an embodiment of the present invention, the chemical reagents include: silver nitrate (AgNO) 3 ) Tetrachloroauric acid (HAuCl) 4 ) And sodium borohydride (NaBH) 4 ）。
Fig. 3 is a schematic structural diagram of the LIBS detection apparatus provided in the present invention, and as shown in fig. 3, the LIBS detection apparatus includes: the system comprises a spectrum collecting head 301, an optical fiber 302, a spectrometer 303, a timing signal transmission line 304, a signal transmission line 305, a laser reflector 306, a laser 307, a laser focusing mirror 308, filter paper 309 adsorbed with mercury ions, a glass slide 310, a displacement platform 311 and a computer 312.
Optionally, the filter paper modified with gold and silver nanoparticles may be placed in a centrifuge tube filled with a liquid to be detected for mercury ions, then the centrifuge tube is placed on an oscillator to oscillate for 10 minutes, then the centrifuge tube is taken out and washed with deionized water for 1-2 times, the filter paper is adhered to a glass slide after natural air drying, and the glass slide adhered with the filter paper is placed on the displacement platform 311 shown in fig. 3 to perform signal detection for mercury ions LIBS.
Alternatively, NaBH may be employed 4 The gold-silver nano alloy is prepared on the surface of the filter paper as a reducing agent, and specifically comprises the following steps: first, 20 mM AgNO was prepared 3 Mixing the two solutions to obtain a mixed solution, taking 4 mL of the mixed solution, placing a filter paper with the size of 10 mM multiplied by 10 mM in the mixed solution, oscillating for 2 minutes, taking out the filter paper, washing the filter paper once by using absolute ethyl alcohol and deionized water respectively, and placing the washed filter paper in a container filled with NaBH with the concentration of 20 mM 4 Placing the filter paper in the solution, oscillating for 1 minute by an oscillator, taking out the filter paper, and washing with deionized water for 1-2 times to obtain the filter paper with the surface modified with the gold-silver nano alloy.
Optionally, 5 mL of mercury ion solutions with different concentrations (e.g., 0 ppm, 0.1 ppm, 1 ppm) may be configured, then the filter paper modified with gold-silver nano alloy is added to the configured mercury ion solutions, one piece of filter paper is added to each solution, then the solution is placed on an oscillator to oscillate for 10 minutes, the filter paper is taken out and naturally air-dried, and the slide glass is attached to a glass slide, the glass slide is placed on a displacement platform 311 shown in fig. 3 to perform mercury ion LIBS signal detection, spectral signals corresponding to the mercury ion solutions with different concentrations are obtained, and a calibration curve is further determined based on the obtained spectral signals and the concentration of the mercury ion solution.
Fig. 4 is a schematic diagram showing the comparison of LIBS spectra when silver nanoparticle modified filter paper and gold-silver nano alloy modified filter paper provided by the present invention are respectively combined with LIBS technology to realize mercury element detection, as shown in fig. 4, the solid line represents the spectrum corresponding to the silver nanoparticle modified filter paper, and the dotted line represents the spectrum corresponding to the gold-silver nano alloy modified filter paper.
Fig. 5 is a schematic diagram of a spectrum for detecting mercury solutions with different concentrations by using gold-silver nano-alloy modified filter paper in combination with the LIBS technology, as shown in fig. 5, corresponding spectra of 0 ppm, 0.1 ppm and 1 ppm of mercury ions are shown, and it can be seen that, as the concentration of mercury ions in the solution increases, the spectral intensity is significantly enhanced at a wavelength of 253.7 nm (Hg I253.7 nm), indicating that the method for detecting mercury elements in a water body provided by the invention is suitable for detecting mercury pollution in the water body.
Specifically, in the embodiment of the present invention, the mercury element in the water body may be detected based on the following steps, including step 5.1 to step 5.7:
step 5.1, mixing the silver nitrate solution and the tetrachloroauric acid solution according to the ratio of 1: 1 proportion to prepare a mixed solution.
And 5.2, adding filter paper with the size of 10 mm multiplied by 10 mm into the mixed solution, placing the mixed solution on an oscillator, oscillating for 2 minutes, taking out the filter paper, and respectively washing the filter paper once by adopting absolute ethyl alcohol and deionized water so as to remove redundant silver nitrate and tetrachloroauric acid on the surface of the filter paper.
And 5.3, placing the treated filter paper in a sodium borohydride solution, placing the sodium borohydride solution on an oscillator, oscillating for 1 minute to enable the sodium borohydride solution to fully react, taking out the treated filter paper, washing the filter paper for 1-2 times by using deionized water, and finally obtaining the filter paper sheet decorated with Au and Ag nano-alloy (gold and silver nano-alloy).
And 5.4, respectively placing the filter paper sheets modified with the Au and Ag nano alloys into N (N is a positive integer greater than 1) mercury solutions with different concentrations, placing the mercury solutions on an oscillator, oscillating for 10 minutes, and taking out.
And 5.5, adhering the filter paper adsorbed with the mercury ions on a glass slide by using a double faced adhesive tape, placing the glass slide on a traditional LIBS device for mercury element detection, and collecting spectral signals at the position of 253.7 nm of Hg I and using the spectral signals for Hg element analysis.
And 5.6, extracting Hg I253.7 nm spectrum signals corresponding to N mercury solutions with different concentrations, and establishing a calibration curve according to the corresponding relation between the mercury solution concentration and the spectrum intensity.
And 5.7, detecting a sample to be detected, synchronously extracting a spectral signal of 253.7 nm Hg I corresponding to the sample to be detected in the step 5.5, and substituting the spectral intensity into the calibration curve established in the step 5.6 to determine the predicted concentration of the sample to be detected.
According to the method for detecting the mercury element in the water body, the mercury element enrichment in the water body is realized through the filter paper modified based on the nano alloy, and the rapid in-situ detection of the mercury element in the water body is realized by combining the laser-induced breakdown spectroscopy technology, so that the detection cost is low, the sensitivity is high, and the operation is simple.
Optionally, the present invention provides a nano-alloy modified filter paper applied to any one of the above methods for detecting elemental mercury in a water body, including:
the gold and silver nanoparticle composite paper comprises first substrate filter paper and gold and silver nanoparticles modified on the first substrate filter paper;
the gold and silver nanoparticles are 40 nm-50 nm in size, and contain gold elements and silver elements in equal proportion.
Specifically, when the method for detecting mercury elements in a water body provided by the invention is used for detecting mercury elements, mercury element enrichment in the water body can be realized by using gold-silver nano-alloy modified filter paper, the gold-silver nano-alloy modified filter paper can comprise first substrate filter paper and gold-silver nano-particles modified on the first substrate filter paper, wherein the size of the gold-silver nano-particles can be 40 nm-50 nm, and the gold-silver nano-particles can contain gold elements and silver elements in equal proportion, that is, the content ratio of the gold elements to the silver elements in the gold-silver nano-particles is 1: 1.
alternatively, the first base filter paper may be any one of ordinary filter papers.
It can be understood that the gold and silver nanoparticles decorated on the first base filter paper are that the gold and silver nanoparticles are attached to the first base filter paper.
According to the nano-alloy modified filter paper provided by the invention, the gold and silver nano-particles are modified on the surface of the first substrate filter paper, so that on one hand, mercury element detection based on the LIBS technology can be better facilitated, and on the other hand, the gold and silver nano-particles have larger specific surface area and can be combined with more mercury elements, thereby greatly improving the enrichment amount of the mercury elements.
Optionally, the present invention provides a nano-alloy modified filter paper applied to any one of the above methods for detecting mercury in a water body, including:
a second substrate filter paper and silver palladium nanoparticles decorated on the second substrate filter paper;
the size of the silver palladium nano particles is 40 nm-50 nm, and the silver palladium nano particles contain silver elements and palladium elements in equal proportion.
Specifically, when the method for detecting mercury elements in a water body provided by the invention is used for detecting mercury elements, mercury element enrichment in the water body can be realized by using silver-palladium nano alloy modified filter paper, the silver-palladium nano alloy modified filter paper can comprise second substrate filter paper and silver-palladium nano particles modified on the second substrate filter paper, wherein the size of the silver-palladium nano particles can be between 40 nm and 50 nm, and the silver-palladium nano particles can contain silver elements and palladium elements in equal proportion, that is, the content ratio of the silver elements to the palladium elements in the silver-palladium nano particles is 1: 1.
alternatively, the second base filter paper may be any one of ordinary filter papers.
It is understood that the silver palladium nanoparticles decorated on the second base filter paper are the silver palladium nanoparticles attached to the second base filter paper.
According to the nano alloy modified filter paper provided by the invention, the silver palladium nano particles are modified on the surface of the second substrate filter paper, so that on one hand, mercury element detection based on the LIBS technology can be better facilitated, and on the other hand, the silver palladium nano particles have larger specific surface area and can be combined with more mercury elements, thereby greatly improving the enrichment amount of the mercury elements.
Optionally, the present invention provides a nano-alloy modified filter paper applied to any one of the above methods for detecting mercury in a water body, including:
a third substrate filter paper and silver platinum nanoparticles decorated on the third substrate filter paper;
wherein the silver platinum nanoparticles have a size of 40 nm to 50 nm; the silver-platinum nano particles contain silver element and platinum element in equal proportion.
Specifically, when the method for detecting mercury elements in a water body provided by the invention is used for detecting mercury elements, mercury element enrichment in the water body can be realized by using silver-platinum nano-alloy modified filter paper, the silver-platinum nano-alloy modified filter paper can comprise third substrate filter paper and silver-platinum nano-particles modified on the third substrate filter paper, wherein the size of the silver-platinum nano-particles can be between 40 nm and 50 nm, and the silver-platinum nano-particles can contain silver elements and platinum elements in equal proportion, that is, the content ratio of the silver elements to the platinum elements in the silver-platinum nano-particles is 1: 1.
alternatively, the third base filter paper may be any conventional filter paper.
It is understood that the silver platinum nanoparticles decorated on the third base filter paper are silver platinum nanoparticles attached to the third base filter paper.
According to the nano-alloy modified filter paper provided by the invention, the silver-platinum nano particles are modified on the surface of the third substrate filter paper, so that on one hand, mercury element detection based on the LIBS technology can be better facilitated, and on the other hand, the silver-platinum nano particles have larger specific surface area and can be combined with more mercury elements, thereby greatly improving the enrichment amount of the mercury elements.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for detecting mercury elements in a water body is characterized by comprising the following steps:
soaking the nano alloy modified filter paper in a mercury-containing solution to be detected for a first preset time period, and then taking out the filter paper to obtain first filter paper adsorbed with mercury ions;
performing mercury element detection on the first filter paper based on a Laser Induced Breakdown Spectroscopy (LIBS) technology to obtain a first spectrum signal corresponding to the mercury-containing solution to be detected;
and determining the mercury concentration of the mercury-containing solution to be detected based on the first spectrum signal and a calibration curve, wherein the calibration curve is used for reflecting the corresponding relation between the mercury concentration and the spectrum signal intensity.
2. The method for detecting mercury elements in a water body according to claim 1, wherein the nano-alloy modified filter paper is a gold-silver nano-alloy modified filter paper;
the gold-silver nano-alloy modified filter paper is prepared by the following steps:
mixing a silver nitrate solution and a tetrachloroauric acid solution to obtain a first mixed solution;
soaking a piece of common filter paper in the first mixed solution for a second preset time, and then taking out the common filter paper to obtain second filter paper;
and soaking the second filter paper in a sodium borohydride solution for a third preset time, and taking out to obtain the gold-silver nano alloy modified filter paper.
3. The method for detecting mercury elements in a water body according to claim 1, wherein the nano-alloy modified filter paper is a silver-palladium nano-alloy modified filter paper;
the filter paper modified by the silver-palladium nano alloy is prepared by the following steps:
mixing a silver nitrate solution with a sodium tetrachloropalladate solution to obtain a second mixed solution;
soaking a piece of common filter paper in the second mixed solution for a fourth preset time, and taking out to obtain a third filter paper;
and soaking the third filter paper in a sodium borohydride solution for a fifth preset time period, and taking out the third filter paper to obtain the silver-palladium nano-alloy modified filter paper.
4. The method for detecting mercury elements in a water body according to claim 1, wherein the nano-alloy modified filter paper is silver-platinum nano-alloy modified filter paper;
the silver-platinum nano alloy modified filter paper is prepared by the following steps:
mixing the silver nitrate solution with the potassium tetrachloroplatinate solution to obtain a third mixed solution;
soaking a piece of common filter paper in the third mixed solution for a sixth preset time, and then taking out to obtain a fourth filter paper;
and soaking the fourth filter paper in a sodium borohydride solution for a seventh preset time, and taking out the fourth filter paper to obtain the silver-palladium nano alloy modified filter paper.
5. The method for detecting mercury elements in a water body according to claim 1, further comprising, before determining the mercury concentration of the mercury-containing solution to be detected based on the first spectrum signal and the calibration curve:
preparing mercury ion solutions with different concentrations;
respectively soaking a plurality of pieces of nano alloy modified filter paper in the mercury ion solutions with different concentrations for an eighth preset time period, and taking out the filter paper to obtain a plurality of pieces of fifth filter paper adsorbed with mercury ions;
performing mercury element detection on the fifth filter paper based on the LIBS technology to obtain second spectrum signals corresponding to the mercury ion solutions with different concentrations;
and fitting the calibration curve based on a plurality of second spectrum signals and the concentration of the mercury ion solution corresponding to each second spectrum signal.
6. The method according to claim 5, wherein fitting the calibration curve based on a plurality of second spectral signals and the concentration of the mercury ion solution corresponding to each second spectral signal comprises:
determining the intensity of the first target spectral signal at the wavelength to which the elemental mercury is characteristically sensitive in each of the second spectral signals;
and fitting the calibration curve based on the intensity of all the first target spectral signals and the concentration of the mercury ion solution corresponding to each second spectral signal.
7. The method for detecting elemental mercury in a body of water according to claim 6, wherein determining the mercury concentration of the mercury-containing solution to be detected based on the first spectral signal and a calibration curve comprises:
determining the intensity of a second target spectral signal at a wavelength to which the elemental mercury is characteristic of in the first spectral signal;
matching the intensity of the second target spectrum signal by using the calibration curve, and determining a target point in the calibration curve, wherein the absolute difference between the intensity of the spectrum signal corresponding to the target point and the intensity of the second target spectrum signal is the minimum;
and determining the mercury concentration corresponding to the target point as the mercury concentration of the mercury-containing solution to be detected.
8. A nano-alloy modified filter paper applied to the method for detecting mercury element in a water body according to any one of claims 1, 2 and 5-7, which is characterized by comprising the following steps:
the gold and silver nanoparticle composite paper comprises first substrate filter paper and gold and silver nanoparticles modified on the first substrate filter paper;
the gold and silver nanoparticles are 40 nm-50 nm in size, and contain gold elements and silver elements in equal proportion.
9. A nano-alloy modified filter paper applied to the method for detecting mercury element in a water body according to any one of claims 1, 3 and 5-7, which is characterized by comprising the following steps:
a second substrate filter paper and silver palladium nanoparticles decorated on the second substrate filter paper;
the size of the silver palladium nano particles is 40 nm-50 nm, and the silver palladium nano particles contain silver elements and palladium elements in equal proportion.
10. A nano-alloy modified filter paper applied to the detection method of mercury element in a water body according to any one of claims 1, 4 and 5 to 7, which is characterized by comprising the following steps:
a third substrate filter paper and silver platinum nanoparticles decorated on the third substrate filter paper;
wherein the silver platinum nanoparticles have a size of 40 nm to 50 nm; the silver-platinum nano particles contain silver element and platinum element in equal proportion.
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