CN108760702B - Detection method of sulfide ions - Google Patents
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- -1 sulfide ions Chemical class 0.000 title claims abstract description 43
- 238000001514 detection method Methods 0.000 title claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 50
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002135 nanosheet Substances 0.000 claims abstract description 42
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 31
- 239000011593 sulfur Substances 0.000 claims abstract description 31
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 19
- 229920001661 Chitosan Polymers 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 13
- 230000005284 excitation Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
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- 230000035945 sensitivity Effects 0.000 abstract description 2
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 10
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 208000003443 Unconsciousness Diseases 0.000 description 1
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- 229910001437 manganese ion Inorganic materials 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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Abstract
The invention discloses a method for detecting sulfur ions, which comprises the steps of synthesizing chitosan serving as a carbon source to obtain a carbon quantum dot solution, mixing the carbon quantum dot solution with a manganese dioxide nanosheet solution to construct a fluorescent probe solution, adding sulfur ion solutions with different concentrations into the fluorescent probe solution, constructing a linear curve by taking the concentration of the sulfur ions as a horizontal coordinate and taking the fluorescence intensity value of a sulfur ion front-back system at a wavelength of 420nm as a vertical coordinate, and further detecting the concentration of the sulfur ions to be detected. The method has the advantages of low cost, high sensitivity, good linear relation, simple and easy operation and good selectivity.
Description
Technical Field
The invention relates to a method for detecting sulfide ions.
Background
With the development of social economy and the aggravation of human production activities, environmental pollution seriously threatens the environment and physical health of human beings depending on survival, especially the emission of sulfur-containing pollutants, so that water and soil resources are polluted, and sulfur ions in sewage are easy to be changed into hydrogen sulfide gas in an acid environment, thereby causing atmospheric pollution. Due to the nature of sulfide ion (or hydrogen sulfide), detection of sulfide ion in environmental pollution and physiology becomes a very practical task. If the content of the hydrogen sulfide in the physiological samples and the living cells can be sensitively and reliably detected, the method can help to understand the action mechanism of the hydrogen sulfide in the pathogenic process.
The concentration of sulfide is an important water pollution index, and in particular even micromolar concentrations of sulfide can poison many aquatic organisms. High sulfide concentrations can irritate the mucous membranes, leading to respiratory paralysis and loss of consciousness. Studies have shown that after hydrogen sulfide is dissolved in water, the concentration of hydrogen sulfide in drinking water is even less than 0.07mg/m3In time, the quality of drinking water is also affected to a certain extent. When the concentration of hydrogen sulfide in water reaches 0.15mg/m3In time, the method has certain influence on the growth of the fish fries newly thrown into the pond and also has certain toxic action on the root systems of plants around the pond. The hydrogen sulfide has toxicity, and the solution of the hydrogen sulfide is acidic and corrosive, so that sulfide stress cracking, hydrogen bubbling, hydrogen induced cracking and the like can be caused on equipment such as pipelines and tanks, and the problems of accelerated corrosion and abrasion of pump impellers, corrosive air holes and the like can be caused.
Therefore, it is necessary to develop a novel detection material that can detect a low concentration of sulfide ions (or hydrogen sulfide).
Disclosure of Invention
The invention provides a method for detecting sulfide ions, which comprises the steps of synthesizing chitosan serving as a carbon source to obtain a carbon quantum dot solution, mixing the carbon quantum dot solution with a manganese dioxide nanosheet solution to construct a fluorescent probe solution, adding sulfide ion solutions with different concentrations into the solution, constructing a linear curve by taking the concentration of the sulfide ions as a horizontal coordinate and the fluorescence intensity value of a sulfide ion front-back system at the wavelength of 420nm as a vertical coordinate, and further detecting the concentration of the sulfide ions to be detected. The method has the advantages of low cost, high sensitivity, good linear relation, simple and easy operation and good selectivity.
The technical scheme adopted by the invention is as follows:
a method for detecting sulfide ions, which is characterized by comprising the following steps:
s1, mixing carbon quantum dot solution taking chitosan as carbon source with MnO2Mixing nanosheet solutions to construct carbon quantum dot/MnO2A nanoplate fluorescent probe solution;
s2 Quantum dot to carbon/MnO2Adding sulfur ion aqueous solutions with different final concentrations into the nanosheet fluorescent probe solution, reacting for 2 hours, and then testing the fluorescence spectrum of each system under the excitation wavelength of 344 nm;
s3, taking the concentration of the sulfur ions as a horizontal coordinate, and taking the fluorescence intensity ratio of the system before and after adding the sulfur ions as a vertical coordinate to construct a linear curve, so as to detect the concentration of the sulfur ions to be detected.
Further, the preparation method of the carbon quantum dot solution with chitosan as a carbon source comprises the following steps: mixing chitosan and deionized water, carrying out hydrothermal reaction for 24h at 180 ℃, centrifuging to obtain supernatant, filtering the supernatant to obtain filtrate, dialyzing the filtrate for 3 h by a dialysis bag with molecular weight cutoff of 3500Da, and taking permeate as the carbon quantum dot solution.
The ratio of the chitosan to the deionized water is 1 g: 45-55 mL.
Further, the MnO2The preparation method of the nanosheet solution comprises the following steps: 2mL of 30% H were measured out separately2O2The solution was mixed with 12mL of a solution having a concentration of 1.0 mol. L-1Diluting the solution to 20mL in a beaker, mixing the solution uniformly, and measuring 10mL of 0.3 mol/L-1MnCl of2·4H2O into a beaker and the resulting dark brown suspension in the chamberStirring at room temperature for 12 hr, centrifuging at 8000r/min for 20min, discarding supernatant, washing precipitate with anhydrous ethanol and deionized water respectively until the precipitate becomes neutral, dispersing the obtained dark brown solid in deionized water, and ultrasonic treating for 1 hr to obtain MnO2A nanosheet solution.
The carbon quantum dot solution and MnO2The volume ratio of the nanosheet solution is 1: 30-35; the MnO2The concentration of the nano-sheet solution is 50-60 mu M.
In step S3, the linear equation of the linear curve is: F/F01.0077+ 0.0205C; linear correlation coefficient R is 0.999, where F0F represents a quantum dot to carbon/MnO, respectively2Adding the fluorescent intensity of the sulfide ion front and back systems at 420nm into the nanosheet fluorescent probe solution; c represents S2-Concentration, in μ M.
The value range of the sulfur ion concentration C is 0-30 mu M. Namely, within the range of 0-30 mu M of the concentration of the sulfur ions, the detection method can present a good linear relation, and further can realize the quantitative detection of the concentration of the sulfur ions.
In the invention, MnO is added2The nanosheets are added into the carbon quantum dot solution, and the fluorescence of the carbon quantum dots is quenched through an internal light filtering effect (IFE) and a Static Quenching Effect (SQE). When to carbon quantum dots/MnO2Adding trace S into the nano-sheet composite system2-Due to S2-And MnO with MnO2The nano sheet is subjected to oxidation-reduction reaction to generate Mn2+Thereby recovering the fluorescence of the carbon quantum dots, and the added S2-Within a certain concentration range, the fluorescence intensity of the solution can be linearly enhanced, and then S is realized2-Trace detection of (2). The method is simple, rapid and effective, and is S2-A novel detection method is provided.
Drawings
FIG. 1 shows the charge directed to the carbon quantum dots/MnO2Adding sulfur ions with different final concentrations into the nanosheet fluorescent probe solution to obtain a fluorescence emission spectrogram of the system under the excitation wavelength of 344 nm;
FIG. 2 is a graph obtained by plotting the concentration of sulfur ions on the abscissa and the fluorescence intensity value of the detection system at 420nm on the ordinate;
FIG. 3 is a graph of linear relationship established by taking the concentration of sulfur ions in the range of 0 to 30 μ M as the abscissa and the ratio of the fluorescence intensity of the detection system at 420nm before and after the addition of sulfur ions as the ordinate;
FIG. 4 is a TEM image of a carbon quantum dot solution with chitosan as a carbon source;
FIG. 5 shows the addition of MnO of different concentrations ranging from 0 to 117. mu.M to a carbon quantum dot solution2A fluorescence emission spectrogram of the system after the nano sheet solution is obtained under the excitation wavelength of 344 nm;
FIG. 6 shows fluorescence intensity of carbon quantum dot solution at 420nm as a function of MnO2A change curve graph of the concentration of the nanosheet solution;
FIG. 7 shows MnO2Ultraviolet absorption spectrum (c) of the nanosheet and fluorescence excitation spectrum (b) of the carbon quantum dot at an emission wavelength of 420nm and emission spectrum (a) at an excitation wavelength of 344 nm;
FIG. 8 shows carbon quantum dots/MnO2A selectivity and anti-interference experimental diagram for detecting sulfide ions by a nano sheet system, wherein 1-10 are respectively Na+、Mg2+、K+、Ca2+、Zn2+、F-、SO4 2-、NO3-、Cl-、CH3COO-。
Detailed Description
Example 1
A method for detecting sulfide ions, which is characterized by comprising the following steps:
s1, mixing 1mL of carbon quantum dot solution using chitosan as carbon source with 32mL of MnO with a concentration of 54 μ M2Mixing nanosheet solutions to construct carbon quantum dot/MnO2A nanoplate fluorescent probe solution;
s2 Quantum dot to carbon/MnO2Adding sulfur ion aqueous solutions with different final concentrations into the nanosheet fluorescent probe solution, reacting for 2 hours, and then testing the fluorescence spectrum of each system under the excitation wavelength of 344nm, as shown in fig. 1; and the concentration of the sulfur ion is plotted as abscissa and the fluorescence intensity value of the system at 420nm is plotted as ordinate, as shown in FIG. 2, from the graph2, it can be seen that as the concentration of the sulfide ion increases, the carbon quantum dot/MnO2The fluorescence intensity of the nanosheets is gradually recovered; and has good linear relation in the range of 0-30 MuM;
s3, taking the concentration of the sulfur ions within the range of 0-30 mu M as a horizontal coordinate, and taking the fluorescence intensity ratio of the system before and after adding the sulfur ions as a vertical coordinate to construct a linear curve, as shown in FIG. 3, the linear equation is as follows: F/F01.0077+ 0.0205C; linear correlation coefficient R is 0.999, where F0F represents a quantum dot to carbon/MnO, respectively2Adding the fluorescent intensity of the sulfide ion front and back systems at 420nm into the nanosheet fluorescent probe solution; c represents S2-The concentration is in the unit of mu M, and the concentration of the sulfur ions to be detected can be further detected according to a linear equation.
The preparation method of the carbon quantum dot solution taking chitosan as the carbon source comprises the following steps: 0.5g of chitosan is taken by an analytical balance, 24ml of deionized water is taken by a measuring cylinder, and the chitosan and the deionized water are placed in a high-pressure reaction kettle for reaction for 24 hours at 180 ℃. Naturally cooling, centrifuging, filtering to obtain supernatant, filtering twice with needle filter to obtain orange chitosan carbon quantum dot solution, dialyzing at room temperature with dialysis bag with molecular weight cutoff of 3500Da for 3 hr to obtain permeate liquid as carbon quantum dot solution, and taking TEM image as shown in FIG. 4 to show that the carbon quantum dot solution has particle size distribution of 1-3.5nm, average particle size of 2.6nm, homogeneous particle size and high dispersivity.
The MnO2The preparation method of the nanosheet solution comprises the following steps: 2mL of 30% H were measured out separately2O2The solution was mixed with 12mL of a solution having a concentration of 1.0 mol. L-1Diluting the solution to 20mL in a beaker, mixing the solution uniformly, and measuring 10mL of 0.3 mol/L-1MnCl of2·4H2Adding O into a beaker, placing the obtained dark brown suspension on a magnetic stirrer at room temperature, stirring for about 12 hours, centrifuging (the rotating speed is 8000r/min, the time is 20 minutes), discarding the supernatant, respectively washing the precipitate with absolute ethyl alcohol and deionized water until the precipitate is neutral after centrifugation, dispersing the obtained dark brown solid in the deionized water, and performing ultrasonic treatment for 1 hour to prepare MnO2Nano meterTablet solution.
Example 2
MnO2Influence of nanosheet solution concentration on fluorescence intensity of carbon quantum dots
After 32mL of manganese dioxide nanosheet solutions with different concentrations in the range of 0-117 mu M are respectively added into 1mL of the carbon quantum dot solution obtained in example 1, the fluorescence spectrum of the system at the excitation wavelength of 344nm is tested, as shown in FIG. 5, and then a graph is drawn by taking the concentration of the manganese dioxide nanosheet as the abscissa and the fluorescence intensity of the system at the wavelength of 420nm as the ordinate, as shown in FIG. 6. As can be seen from FIGS. 5 and 6, the solution of the carbon quantum dots has strong fluorescence at 420nm, and MnO was added2After nanosheet, the fluorescence of the system is rapidly quenched. And the fluorescence intensity of the system can follow MnO2The concentration of the nanosheets increased and gradually decreased.
Example 3
Carbon quantum dot/MnO2Discussion of sulfur ion detection mechanism by nanosheet fluorescent probe
In order to research the mechanism of fluorescence quenching of the system, MnO is continuously researched2The ultraviolet absorption spectrum of the nanosheets and the fluorescence excitation spectrum at an emission wavelength of 420nm and the emission spectrum at an excitation wavelength of 344nm of the carbon quantum dots are shown in fig. 7. As can be seen from FIG. 7, MnO2The nano-sheet has a wide ultraviolet absorption band in the range of 200 nm-600 nm, such as curve c in the figure, and the peak value is 380 nm. The quenching efficiency is high because the excitation spectrum b and the emission spectrum a of the carbon quantum dots are just equal to the MnO prepared2The UV absorption spectra of the nanoplates overlap for a large part, which means MnO2The nanoplatelets absorb the excitation light or emission light of the carbon quantum dots, causing the excitation light or emission light to occur between the two
Resonance Energy Transfer (FRET) and internal light filtering effect (IFE) to attenuate the fluorescence of the carbon quantum dots; when MnO is present2After the nano sheet is added into the carbon quantum dot solution, the nano sheet and the carbon quantum dot solution can be combined to generate a relatively stable composite system, and the structure is obtained according to the principle of Static Quenching Effect (SQE)The fluorescence of the system can be weakened; accordingly, MnO2The efficiency of quenching the carbon quantum dots by the nanosheets is relatively high. When a trace amount of S is added to the system2-Due to S2-And MnO with MnO2Oxidation-reduction reaction occurs to generate bivalent manganese ions in the solution, thereby leading the carbon quantum dots/MnO2The fluorescence intensity of the system is recovered and enhanced, and the enhanced fluorescence intensity is within a certain range of S2-The concentration of the ions is in a linear relationship, and a detection S is established according to the linear relationship2-And (3) an ionic method.
Example 4
Selectivity experiment and anti-interference experiment
A stable and excellent fluorescent probe must have good selectivity and anti-interference capability. To explore the carbon quantum dot/MnO2The anti-interference capability of the nano-sheet fluorescent probe is realized by selecting some common ions such as Na in the experiment+、K+、Mg2+、Ca2+、Zn2 +、F-、Cl-、SO4 2-、NO3 -、CH3COO-To perform interference experiments. Wherein the concentration of the above ions is 50. mu.M, S2-The concentration was 18. mu.M.
The experimental method comprises the following steps: 1mL of carbon quantum dot solution taking chitosan as a carbon source and 32mL of MnO with the concentration of 54 mu M2Mixing nanosheet solutions to construct carbon quantum dot/MnO2A nanoplate fluorescent probe solution; to carbon quantum dots/MnO2Respectively adding 50 mu M of Na into the nano-sheet fluorescent probe solution+、K+、Mg2+、Ca2+、Zn2+、F-、Cl-、SO4 2-、NO3 -、CH3COO-The fluorescence spectrum of the test system at the excitation wavelength of 344nm was measured, and then 18. mu.M of S was added to the test systems, respectively2-The fluorescence spectrum of the test system at the excitation wavelength of 344nm is plotted with the interfering ions as abscissa and the fluorescence intensity at the wavelength of 420nm as ordinate.
The experimental results are shown in FIG. 8, and the addition of sulfur ions maximizes the fluorescence rising degree of the systemAnd, in addition to sulfide ions, other ions are paired with carbon quantum dots/MnO2The effect of the fluorescence rising degree of the composite system is small and almost negligible. The experimental results show that the carbon quantum dots/MnO2The complex system has good selectivity and anti-interference performance when detecting the sulfur ions. Thus, the invention discloses carbon quantum dots/MnO2The nano-sheet fluorescent probe system is suitable for S2-The method has the capability of detecting the sulfur ions in the complex water sample.
The above detailed description of a method for detecting sulfide ions with reference to the embodiments is illustrative and not restrictive, and several embodiments may be enumerated within the scope of the limitations, so that changes and modifications may be made without departing from the spirit of the present invention.
Claims (4)
1. A method for detecting sulfide ions, which is characterized by comprising the following steps:
s1, mixing carbon quantum dot solution taking chitosan as carbon source with MnO2Mixing nanosheet solutions to construct carbon quantum dot/MnO2A nanoplate fluorescent probe solution;
s2 Quantum dot to carbon/MnO2Adding sulfur ion aqueous solutions with different final concentrations into the nanosheet fluorescent probe solution, reacting for 2 hours, and then testing the fluorescence spectrum of each system under the excitation wavelength of 344 nm;
s3, taking the concentration of the sulfur ions as a horizontal coordinate, adding the fluorescence intensity ratio of the sulfur ion front and back system at 420nm as a vertical coordinate to construct a linear curve, and further detecting the concentration of the sulfur ions to be detected;
the carbon quantum dot solution and MnO2The volume ratio of the nanosheet solution is 1: 30-35; the MnO2The concentration of the nanosheet solution is 50-60 mu M;
in step S3, the linear equation of the linear curve is:F/F 0=1.0077+0.0205C(ii) a Linear correlation coefficient R =0.999, where F0F represents a quantum dot to carbon/MnO, respectively2Adding the fluorescent intensity of the sulfide ion front and back systems at 420nm into the nanosheet fluorescent probe solution; c representsS2-Concentration, in μ M.
2. The detection method according to claim 1, wherein the preparation method of the carbon quantum dot solution using chitosan as a carbon source comprises the following steps: mixing chitosan and deionized water, carrying out hydrothermal reaction for 24h at 180 ℃, centrifuging to obtain supernatant, filtering the supernatant to obtain filtrate, dialyzing the filtrate for 3 h by a dialysis bag with molecular weight cutoff of 3500Da, and taking permeate as the carbon quantum dot solution.
3. The detection method according to claim 2, wherein the ratio of chitosan to deionized water is 1 g: 45-55 mL.
4. The detection method according to claim 1, wherein the concentration C of the sulfide ion is in a range of 0 to 30 μ M.
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