CN110567950B - Method for detecting sulfur ions - Google Patents
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- CN110567950B CN110567950B CN201910873489.6A CN201910873489A CN110567950B CN 110567950 B CN110567950 B CN 110567950B CN 201910873489 A CN201910873489 A CN 201910873489A CN 110567950 B CN110567950 B CN 110567950B
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- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
Abstract
The invention discloses a method for detecting sulfur ions. The method comprises the following steps: adding ascorbic acid, a mercuric nitrate solution and a sulfur ion solution into a silver nanoparticle solution diluted by a certain amount to prepare a reaction system, and reacting for 2-60 min; in the reaction system, the concentration of the ascorbic acid is 2-70 mu M, and the concentration of the mercury ions is 0.175-1750 mu g/L; and detecting the concentration of the sulfur ions by using an ultraviolet visible light photometer. The method for detecting the sulfide ions has the advantages of high sensitivity and selectivity, simplicity in operation and the like, and the lower detection limit can reach 8.3 nM.
Description
Technical Field
The invention relates to the technical field of detection methods, in particular to a method for detecting sulfur ions based on silver-mercury composite nanoparticles.
Background
Sulfide ions pose a significant threat to human health and the environment, and sulfide is a ubiquitous environmental pollutant that is released from industries such as paper, petrochemicals, and leather. The pollution to the environment caused by a large amount of sulfide entering water and air is more and more serious, so that the content of the sulfide in the environment needs to be monitored.
The sulfur ion is not only an important environmental index, but also the molecular hydrogen sulfide is a gas signal molecule in the human body, is closely related to the health of the human body, and is widely distributed in the human body and other biological systems and ecosystems. Research shows that endogenous hydrogen sulfide is related to many diseases and plays an important role in the body, such as: the cAMP signal channel can be activated by nitric oxide to enable tissues to generate hydrogen sulfide, and D, L-propargyl glycine is injected into the abdominal cavity to prevent the tissues from generating hydrogen sulfide and increase the blood pressure; the blood plasma hydrogen sulfide level of the hypertensive patient with renal damage is obviously reduced compared with that of a normal person, and the hypertension is more serious; when the endogenous hydrogen sulfide is insufficient, the vasodilation function of the vascular smooth muscle is reduced, and the cardiac muscle strength is increased, so that the occurrence of coronary heart disease is caused; the plasma hydrogen sulfide concentration of patients with coronary heart disease is reduced by half compared with normal people, and the reduction of the plasma hydrogen sulfide level can be related to coronary artery vascular disease; the non-steroidal anti-inflammatory drugs can block the expression of cystathionine gamma lyase, reduce the concentration of hydrogen sulfide and weaken the positive effect on the stomach. Therefore, the detection of sulfide ions is a very important thing.
In the prior art, there are many methods for detecting sulfide ions, such as: electrochemical methods, spectrophotometric methods, capillary electrophoresis methods, chromatography, and the like. The electrochemical method is used for measuring the sample liquid according to the relation between certain parameters in the chemical battery and the concentration of the sample liquid, has the advantages of high sensitivity, simple operation, wide measurement range and the like, but has poor selectivity; the method for detecting the sulfide in the water quality in the national standard is a methylene blue spectrophotometry, and has the characteristics of low cost, simple equipment operation, high detection speed and the like, but the method has more interference factors and has poor detection effect on complex samples; the capillary electrophoresis method can separate different components in a sample, is commonly used for measuring complex samples, has the remarkable characteristics of small sample usage amount and high selectivity, can be used for detecting various anions, and is used for analyzing different matrix samples. In the related technology, different sulfur-containing anion samples are analyzed by adopting a capillary electrophoresis method, and the lowest detection limit of the sulfur ions is measured to be 0.2 mg/L; the chromatography has the characteristics of good separation effect, high sensitivity, high analysis speed and the like, but the operation is more complex.
In view of the above, it is necessary to provide a method for detecting sulfide ions with high sensitivity and selectivity and simple operation.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a method for detecting sulfur ions based on silver-mercury composite nanoparticles, which has the advantages of higher sensitivity and selectivity, simplicity in operation and the like.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method of detecting sulfide ions, comprising the steps of:
step S1: adding ascorbic acid, a mercuric nitrate solution and a sulfur ion solution into a silver nanoparticle solution diluted by a certain amount to prepare a reaction system, and reacting for 2-60 min; in the reaction system, the concentration of the ascorbic acid is 2-70 mu M, and the concentration of the mercury ions is 0.175-1750 mu g/L;
step S2: and detecting the concentration of the sulfur ions by using an ultraviolet visible light photometer.
Further, the concentration of ascorbic acid in the reaction system was 17.5 to 70. mu.M.
Further, the concentration of ascorbic acid in the reaction system was 35. mu.M.
Furthermore, the concentration of mercury ions in the reaction system is 0.175-17.5. mu.g/L.
Further, the concentration of mercury ions in the reaction system was 1.75. mu.g/L.
Furthermore, the pH value in the reaction system is 3-8.
Further, the reaction system had a pH of 7.
Further, in step S1, the reaction time was 18 min.
Further, the preparation method of the silver nanoparticles comprises:
mixing the following components in parts by volume, and stirring to obtain a premix: 2.1 parts of water, 2 parts of 1% sodium citrate, 0.5 part of 1% silver nitrate solution and 0.4 part of 20mmol/L NaCl;
adding 0.1 part of ascorbic acid with the concentration of 0.1mol/L into 95 parts of boiling water according to the parts by volume, and adding 5 parts of premix until the solution is yellow; reacting for a certain time until the temperature of the system is reduced to 65-90 ℃, adding 1.2 parts of silver nitrate solution with the concentration of 1%, and darkening the color to obtain the silver nano-particles.
Compared with the prior art, the method for detecting the sulfur ions provided by the invention has the beneficial effects that:
firstly, the silver-mercury composite nano particles are adopted to detect the concentration of sulfur ions, when the sulfur ions are added into a silver-mercury composite system, the original silver-mercury alloy structure is destroyed, a new compound is formed, and the color and the light absorption value of the system are obviously changed. The local plasma resonance absorption peak disappears with the addition of a large amount of sulfur ions, and the color changes obviously when the concentration of the sulfur ions is higher, the color changes from yellow to dark yellow or orange to the naked eye, and changes to dark blue when the concentration is higher. Experiments show that the change of the light absorption value caused by adding the sulfur ions and the concentration of the sulfur ions are in a linear relationship in a certain range. The lower limit of the detection method for the sulfide ions is 8.3 nM.
Secondly, the method for detecting the sulfur ions has good selectivity, and PO 4 3- 、C 5 H 7 O 5 COO - 、SO 4 2- 、CH 3 COO - 、CO 3 2- The plasma anion does not substantially interfere with the detection of the sulfide ion.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic diagram of a mechanism for detecting sulfur ions by silver-mercury composite nanoparticles;
FIG. 2 is a diagram of the UV-Vis spectrum of the reaction of sulfur ions under different conditions;
FIG. 3 is an electron micrograph of different nanoparticles;
FIG. 4 is a graph of the effect of ascorbic acid on the detection of sulfide ions;
FIG. 5 is a graph of the effect of mercury ion concentration on sulfur ion detection;
FIG. 6 is a graph of the effect of pH on detection of sulfide ions;
FIG. 7 is a graph of the effect of reaction time on sulfur ion detection;
FIG. 8 is a light absorption curve of a reaction system with different concentrations of sulfide ions;
FIG. 9 is a partial graph of FIG. 8;
FIG. 10 is a graph of the effect of different anions on detection of sulfide ions.
Detailed Description
In order to make the technical solutions in the embodiments of the present invention better understood and make the above objects, features, and advantages of the present invention more comprehensible, specific embodiments of the present invention are described below with reference to the accompanying drawings.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The chemical reagents and test instruments used in the invention are referred to as follows:
chemical reagents are shown in table 1:
table 1: chemical reagent
The experimental apparatus is shown in table 2:
table 2: laboratory apparatus
Example 1 preparation of silver nanoparticles
The preparation method of the silver nanoparticles comprises the following steps:
mixing the following components in parts by volume, and stirring to obtain a premix: 2.1 parts of water, 2 parts of 1% sodium citrate, 0.5 part of 1% silver nitrate solution and 0.4 part of 20mmol/L NaCl; wherein the premixing time is 5 min;
adding 0.1 part of ascorbic acid with the concentration of 0.1mol/L into 95 parts of boiling water according to the parts by volume, and adding 5 parts of pre-mixed solution prepared in advance after 5min until the solution is yellow; reacting for a certain time until the temperature of the system is reduced to 65-90 ℃, adding 1.2 parts of silver nitrate solution with the concentration of 1%, and darkening the color to obtain the silver nano-particles. Preferably, in this example, the reaction is carried out for 0.5 hour, and 1.2 parts of 1% silver nitrate solution is added when the temperature of the system is reduced to 80 ℃.
Example 2 sulfide ion detection
A method of detecting sulfide ions, comprising the steps of:
step S1: adding ascorbic acid, a mercuric nitrate solution and a sulfur ion solution into a silver nanoparticle solution diluted by a certain amount to prepare a reaction system, and reacting for 2-60 min; in the reaction system, the concentration of the ascorbic acid is 2-70 mu M, and the concentration of the mercury ions is 0.175-1750 mu g/L;
step S2: and detecting the concentration of the sulfur ions by using an ultraviolet visible light photometer.
Fig. 1 is a schematic diagram illustrating a mechanism of detecting sulfur ions by silver-mercury composite nanoparticles. The mercury ions are reduced into mercury atoms by ascorbic acid and combined with the silver nanoparticles to form silver-mercury composite nanoparticles. When sulfur ions are added into the silver-mercury alloy system, the light absorption value is obviously reduced, and the local plasma resonance absorption peak disappears along with the addition of a large amount of sulfur ions. This is because the addition of sulfur ions, which react with the silver amalgam, forms new compounds that destroy the original silver amalgam structure. When the concentration of the sulfide ions is higher, the color change is obvious, the color can be changed into dark yellow or orange by naked eyes, and the color is changed into dark blue when the concentration is higher. The change of the light absorption value caused by adding the sulfur ions and the concentration of the sulfur ions are in a linear relation in a certain range, and the content of the sulfur ions in the sample is detected according to the relation.
Examples 3 to 6
Four sets of comparative experiments were designed based on the method of detecting sulfide ions of example 2 to form examples 3-6.
The specific comparative experimental method is as follows:
taking 42 mL centrifuge tubes, and numbering the centrifuge tubes as A, B, C, D;
each tube was charged with 1.83mL of ten-fold diluted silver nanoparticles prepared in example 1 and 35. mu.L of 0.1M ascorbic acid, 35. mu.L of 100. mu.g/L mercuric nitrate for B and C, and 100. mu.L of 0.1mM sodium sulfide for C and D, in a total volume of 2mL, the remainder was made up with ultrapure water, reacted for 18min, and scanned with an ultraviolet-visible spectrophotometer at 800nm range of 300-.
The experimental results of examples 3-6 were compared and shown in FIG. 2, which is a graph of UV-Vis spectra of the reaction of sulfide ion under different conditions. Wherein, the curve a represents an ultraviolet-visible spectrum diagram under an AgNPs + AA reaction system; curve b represents the ultraviolet-visible spectrum diagram under the AgNPs + AA + Hg reaction system; curve c represents the ultraviolet-visible spectrum diagram under the AgNPs + AA + S reaction system; and the curve d represents an ultraviolet-visible spectrum diagram under an AgNPs + AA + Hg + S reaction system.
As can be seen from FIG. 2, when sulfide ions are added to the silver nanoparticle solution, the change of the light absorption value of the silver-mercury alloy reaction with the sulfide ions is significantly greater than that of the silver nanoparticle solution reaction with the sulfide ions. Due to the excessively high concentration of the sulfur ions, the absorption peak of the silver-mercury composite nanoparticles disappears. Under the same conditions, the silver-mercury alloy nanoparticles react with sulfur ions more sensitively, thereby illustrating the feasibility of using the silver-mercury composite nanoparticles to detect sulfur ions.
FIG. 3 shows an electron microscope image of different nanoparticles; wherein (a) is an electron microscope image of an AgNPs system; (b) is AgNPs + AA + Hg 2+ Electron micrograph of the system; (c) is AgNPs + AA + Hg 2+ +S 2- Electron micrograph of the system. As can be seen from fig. 3, the silver nanoparticles and the silver-mercury composite nanoparticles are spheroidal, and it can be clearly observed that the particle size of the nanoparticles increases with the addition of mercury ions, but the shape is still spheroidal. And the reaction with sulfur ions is continued, and the nano particles are agglomerated.
And as can be seen from an electron microscope image, the distribution of silver and mercury in the silver-mercury composite nano particles is not a core-shell structure, the silver element is distributed in a large amount, and the mercury element is less but is distributed uniformly.
As can be seen from the comparative experiments of examples 3-6, the detection effect of the silver-mercury composite nanoparticles for detecting sulfur ions is better than that of the silver nanoparticles.
Based on this, the condition parameters are optimized by specific experiments as follows. The condition optimization experiment is a single-factor optimization experiment comprising ascorbic acid, mercury ion concentration, pH value and reaction time in a system containing a certain concentration of sulfur ions.
Examples 7 to 12
Effect of ascorbic acid concentration: when the concentration of the reducing agent ascorbic acid is different, the detection is influenced by the influence on the reaction rate, so that the concentration of the ascorbic acid needs to be optimized to obtain the optimal concentration.
The experimental conditions were as follows:
the total volume of the reaction was 2mL, 1.83mL of silver nanoparticles diluted ten times was added, 35. mu.L of ascorbic acid (0.125 mM, 0.25mM, 0.5mM, 1mM, 2mM, and 4mM) prepared in different concentrations were added to different centrifuge tubes, respectively, so that the final concentrations in the reaction system were 2.1875. mu.M, 4.375. mu.M, 8.75. mu.M, 17.5. mu.M, 35. mu.M, and 70. mu.M, after mixing, 35. mu.L of 100. mu.g/L mercuric nitrate was added, after mixing, the reaction was carried out at room temperature for 5 minutes, and finally 100. mu.L of 0.1mM sulfide ion was added, and the reaction was carried out at room temperature for 18 minutes.
FIG. 4 shows the effect of ascorbic acid on the detection of sulfide ions. As can be seen from fig. 4, the ascorbic acid concentration increased, and the absorbance difference Δ a also increased, and when the ascorbic acid concentration increased to 35 μ M, the change in Δ a was no longer significant, and at this time, the silver-mercury composite nanoparticles had been sufficiently formed, determining that the final concentration of ascorbic acid in the reaction system was optimal at 35 μ M.
Examples 13 to 17
The influence of the concentration of mercury ions, the experimental conditions were as follows:
the total volume of the reaction system is 2mL, 1.83mL of silver nanoparticles which are diluted ten times and 35 mu L of 2mM ascorbic acid are added, the mixture is mixed evenly, 35 mu L of mercury nitrate with the concentration of 10 mu g/L, 100 mu g/L, 1000 mu g/L, 10000 mu g/L and 100000 mu g/L are added into different centrifuge tubes respectively, and the mixture is placed at room temperature for reaction for 5 minutes after being mixed fully. Finally, 100. mu.L of 0.1mM sulfide ion was added and the reaction was carried out at room temperature for 18 min.
FIG. 5 shows the effect of mercury ion concentration on sulfur ion detection. As can be seen from FIG. 5, as the concentration of mercury ions increases, Δ A gradually increases to a maximum at a final concentration of 1.75. mu.g/L, and then Δ A decreases, so that the final concentration of mercury ions is most preferable at 1.75. mu.g/L.
The concentration of mercury ions is too low to form enough silver-mercury composite nano particles, and the reaction with sulfur ions is naturally not sensitive; the mercury ion concentration is too high, the silver nanoparticles can be completely permeated by mercury simple substances to be wrapped, and the characteristic absorption peak of the silver nanoparticles can disappear, so that the mercury ion concentration is not too low or too high, and is moderate to be the best.
Examples 18 to 23
The influence of the pH value, the experimental conditions are as follows:
the original pH of the silver nanoparticles after ten-fold dilution was 6.01. The total volume of the reaction was 2mL, 1.83mL of silver nanoparticles diluted ten times and 35. mu.L of 2mM ascorbic acid were added, mixed well, 35. mu.L of 100. mu.g/L mercury ions were added for reaction for 5 minutes, and then 100. mu.L of 0.1mM sulfur ions were added for reaction at room temperature for 18 min. The pH of the reaction solution was 3.0 to 8.0, and the equidistance was 1.0 (3.0, 4.0, 5.0, 6.0, 7.0, 8.0, respectively).
FIG. 6 shows the effect of pH on the detection of sulfide ions. As can be seen from FIG. 6, in the range of pH 3.0 to 8.0, Δ A increases with increasing pH, and is maximized to pH 7.0, and then Δ A gradually decreases. Therefore, in the range of pH 3.0 to 8.0, the optimum reaction pH is 7.0.
Example 24
The reaction time was affected by the following reaction conditions:
the total volume of the reaction is 2mL, the pH value is 7.0, 1.83mL of silver nanoparticles diluted ten times and 35 muL of 2mM ascorbic acid are added, the mixture is mixed evenly, 35 muL of 100 mug/L mercury ions are added for reaction for 5 minutes, then 100 muL of 0.1mM sulfur ions are added for reaction at room temperature, the scanning frequency is set to be 120 s/time, and the total time is 30 min.
FIG. 7 shows the effect of reaction time on detection of sulfide ions. As can be seen from FIG. 7, as the reaction proceeded, Δ A gradually increased, indicating that the reaction proceeded all the time and stabilized by 18min, indicating that the sulfide ion had reacted almost completely, and finally, 18min was determined as the reaction time of the experiment.
It should be noted that the reaction tends to be stable after 18min, so that a certain period of time after 30min also falls within the scope of the present invention, including any time from 30min to 60 min.
Examples 25 to 34
And (4) making a standard curve according to the determined optimized experimental conditions.
The total reaction volume is 2mL, the pH is 7.0, 1.83mL of silver nanoparticles diluted ten times and 35. mu.L of ascorbic acid of 2mmol/L are added, the mixture is mixed uniformly, 35. mu.L of 100. mu.g/L mercury ions are added for reaction for 5 minutes, then 100. mu.L of 0.5. mu.M, 1. mu.M, 5. mu.M, 10. mu.M, 25. mu.M, 50. mu.M, 100. mu.M, 250. mu.M, 500. mu.M and 1000. mu.M sulfur ions are respectively added, the final concentration of the sulfur ions in the reaction system is 0.025. mu.M, 0.05. mu.M, 0.25. mu.M, 0.5. mu.M, 1.25. mu.M, 2.5. mu.M, 5. mu.M, 12.5. mu.M, 25. mu.M and 50. mu.M, and the reaction time is 18 min. When the added sulfide ion increases, the color of the mixed solution changes from pale yellow to orange yellow due to the increase of the reaction substrate.
Based on the reaction results of examples 25 to 34, a plot of the concentration of sulfide ion versus absorbance difference Δ A was prepared. Please refer to fig. 8 and fig. 9, wherein fig. 8 is a graph showing the variation of absorbance for different concentrations of sulfide ions; fig. 9 is a partial graph of fig. 8. As can be seen from fig. 8 and 9, as the concentration of the sulfur ions increases, Δ a also increases, and after the concentration of the sulfur ions reaches a certain value, Δ a does not change substantially, and at this time, the concentration of the sulfur ions is relatively high, the nanoparticles aggregate, and the characteristic absorption peak disappears; in the range of 0.0083-2.5 mu M, the linear relation is better, and the linear equation y is 0.1604x +0.044 (R) 2 0.994), the lower detection limit of this method is 8.3 nM.
As can be seen from the curves in fig. 8 and 9, the method for detecting sulfide ions provided by the present invention has high sensitivity.
Examples 35 to 42
Selectivity experiments, reaction conditions were as follows:
to test the selectivity of this method, several common anionic POs were selected 4 3- 、C 5 H 7 O 5 COO - 、SO 4 2- 、CH 3 COO - 、CO 3 2- 、Br - And NO 2 - The mixture was added to the test environment to give a final concentration of 25. mu.M of all ions and a final concentration of 2.5. mu.M of sulfide ions, and an interference test was conducted.
The total reaction volume is 2mL, 1.83mL silver nanoparticles diluted ten times are added firstly, then 35 mu L2 mmol/L ascorbic acid is added, the mixture is mixed evenly, 35 mu L100 mu g/L mercury ions are added for reaction for 5 minutes, then 100 mu L different anions with the concentration of 0.5mmol/L and 100 mu L sulfide ions with the concentration of 50 mu M are added respectively for reaction for 18 minutes at room temperature.
FIG. 10 shows the effect of different anions on the detection of sulfide ions. As can be seen from FIG. 10, PO 4 3- 、C 5 H 7 O 5 COO - 、SO 4 2- 、CH 3 COO - 、CO 3 2- Has no influence on the detection of sulfur ions, i.e. Br - 、NO 2 - The effect on the detection of sulfide ions is slight, but the effect is negligible at very low concentrations. The results show that PO 4 3- 、C 5 H 7 O 5 COO - The anions basically do not interfere the detection of the sulfur ions, and the method for detecting the sulfur ions has good selectivity on the sulfur ions.
Examples 43 to 45
Sample analysis, conditions were as follows:
sample preparation: sample (I) pond water before four religions of southern forestry science and technology university;
sample (II) Wahaha barreled drinking water;
sample (iii) plasma;
sample treatment: respectively adding 30 mu M of sulfur ions into the sample (I) and the sample (II), and diluting the sample (III) by 30 times;
reaction conditions are as follows: the total reaction volume is 2mL, the pH value is 7.0, 1.83mL of silver nanoparticles diluted by 10 times is taken, 35 mu L of 2mmol/L ascorbic acid is added, the mixture is uniformly mixed, 35 mu L of 100 mu g/L mercuric nitrate is added for reaction for 5 minutes, finally 100 mu L of sample solution is respectively added for reaction for 18 minutes, and the ultraviolet visible absorption spectrum is measured.
And (3) detection results: the concentration of the sulfur ions in the sample (I) is 1.607 MuM, and the recovery rate is 107.1 percent; the concentration of the sulfur ions in the sample (II) is 1.452 mu M, and the recovery rate is 96.8 percent; the concentration of sulfur ions in sample (III) was 58.29. mu.M. The detection result further shows that the method for detecting the sulfur ions has higher sensitivity.
It should be noted that, herein, the "silver-mercury composite nanoparticles" and the "silver-mercury alloy nanoparticles" are the same substance, and thus, the "silver-mercury composite nanoparticles" and the "silver-mercury alloy nanoparticles" may be used in combination.
Compared with the prior art, the method for detecting the sulfur ions provided by the invention has the beneficial effects that:
firstly, the silver-mercury composite nano particles are adopted to detect the concentration of sulfur ions, when the sulfur ions are added into a silver-mercury composite system, the original silver-mercury alloy structure is destroyed, a new compound is formed, and the color and the light absorption value of the system are obviously changed. The local plasma resonance absorption peak disappears with the addition of a large amount of sulfur ions, and the color changes obviously when the concentration of the sulfur ions is higher, the color changes from yellow to dark yellow or orange to the naked eye, and changes to dark blue when the concentration is higher. Experiments show that the change of the light absorption value caused by adding the sulfur ions and the concentration of the sulfur ions are in a linear relationship in a certain range. The lower limit of the detection method for the sulfide ions is 8.3 nM.
Secondly, the method for detecting the sulfur ions has good selectivity, and PO 4 3- 、C 5 H 7 O 5 COO - 、SO 4 2- 、CH 3 COO - 、CO 3 2- The plasma anion does not substantially interfere with the detection of the sulfide ion.
The embodiments of the present invention are described in detail above with reference to the drawings, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (8)
1. A method for detecting sulfide ions, comprising the steps of:
step S1: adding ascorbic acid, a mercuric nitrate solution and a sulfur ion solution into a silver nanoparticle solution diluted by a certain amount to prepare a reaction system, and reacting for 2-60 min; adding ascorbic acid into the silver nanoparticle solution, uniformly mixing, adding mercury nitrate, fully mixing, reacting at room temperature to generate silver-mercury composite nanoparticles, wherein the distribution of silver and mercury in the silver-mercury composite nanoparticles is a non-core-shell structure, finally adding sulfide ions, and reacting at room temperature for a period of time; in the reaction system, the concentration of the ascorbic acid is 2-70 mu M, and the concentration of the mercury ions is 0.175-17.5 mu g/L;
step S2: and detecting the light absorption value by adopting an ultraviolet-visible spectrophotometer, wherein the light absorption value change caused by adding the sulfur ions and the concentration of the sulfur ions form a linear relation in a certain range, and the content of the sulfur ions in the sample is detected according to the relation.
2. The method for detecting sulfide ions according to claim 1, wherein the concentration of ascorbic acid in the reaction system is 17.5 to 70. mu.M.
3. The method for detecting sulfide ions according to claim 2, wherein the concentration of ascorbic acid in the reaction system is 35. mu.M.
4. The method for detecting sulfur ions according to claim 1, wherein the concentration of mercury ions in the reaction system is 1.75 μ g/L.
5. The method for detecting sulfide ions according to claim 1, wherein the reaction system has a pH of 3 to 8.
6. The method for detecting sulfide ions according to claim 5, wherein the reaction system has a pH of 7.
7. The method for detecting sulfide ions according to claim 1, wherein in step S1, sulfide ions are added at last, and the reaction time is 18min at room temperature.
8. The method for detecting sulfide ions according to any one of claims 1 to 7, wherein the silver nanoparticles are prepared by a method comprising:
mixing the following components in parts by volume, and stirring to obtain a premix: 2.1 parts of water, 2 parts of 1% sodium citrate, 0.5 part of 1% silver nitrate solution and 0.4 part of 20mmol/L NaCl;
adding 0.1 part of ascorbic acid with the concentration of 0.1mol/L into 95 parts of boiling water according to the parts by volume, and adding 5 parts of premix until the solution is yellow; reacting for a certain time until the temperature of the system is reduced to 65-90 ℃, adding 1.2 parts of silver nitrate solution with the concentration of 1%, and darkening the color to obtain the silver nano-particles.
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| CA2489673A1 (en) * | 2003-12-09 | 2005-06-09 | Medx Health Corp. | Shape-adaptable and spectral-selective distributed light sources using passive host medium |
| CN107991273A (en) * | 2017-09-11 | 2018-05-04 | 齐齐哈尔大学 | A kind of imdazole derivatives class mercury ion and sulphion relay fluoroscopic examination and application method |
| CN109211856A (en) * | 2018-09-11 | 2019-01-15 | 安徽师范大学 | A method of being based on Ce(III)/AgNCs composite Nano clustered materials detection sulphion |
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| "One-pot preparation of graphene–Ag nano composite for selective and environmentally-friendly recognition of trace mercury(II)";Zhengquan Yan et al.，;《RSC ADVANCES》;20161104;第6卷(第111期);第109857-109861页 * |
| "pH triggered green synthesized silver nanoparticles toward selective colorimetric detection of kanamycin and hazardous sulfide ions";Rohit Kumar Singh et al.，;《JOURNAL OF MOLECULAR LIQUIDS 》;20180811;第269卷;第269-277页 * |
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