CN108267412B - Rapid and reusable hexavalent chromium ion detection system and method - Google Patents
Rapid and reusable hexavalent chromium ion detection system and method Download PDFInfo
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000001514 detection method Methods 0.000 title claims abstract description 75
- 229910001430 chromium ion Inorganic materials 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 199
- LNTHITQWFMADLM-UHFFFAOYSA-N anhydrous gallic acid Natural products OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229940074391 gallic acid Drugs 0.000 claims abstract description 59
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 59
- 239000002105 nanoparticle Substances 0.000 claims abstract description 54
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 51
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 51
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 40
- 238000002835 absorbance Methods 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 239000001913 cellulose Substances 0.000 claims abstract description 11
- 229920002678 cellulose Polymers 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 239000012086 standard solution Substances 0.000 claims description 45
- -1 gallic acid modified gold Chemical class 0.000 claims description 34
- 239000001509 sodium citrate Substances 0.000 claims description 26
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 26
- 239000012490 blank solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 18
- 229910052737 gold Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000003086 colorant Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000703 high-speed centrifugation Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 239000012088 reference solution Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000004737 colorimetric analysis Methods 0.000 abstract description 2
- 238000011481 absorbance measurement Methods 0.000 abstract 1
- 238000002798 spectrophotometry method Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 10
- 239000011651 chromium Substances 0.000 description 9
- 239000012528 membrane Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000020680 filtered tap water Nutrition 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
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- G—PHYSICS
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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Abstract
A quick and reusable hexavalent chromium ion detection system and a method belong to the technical field of chemical analysis, and the detection system comprises methylene blue solution, gallic acid modified gold nanoparticle solution and NaBH4A solution; the method comprises the following steps: adding a water sample to be detected into a mixed solution consisting of a methylene blue solution and a gallic acid modified gold nanoparticle solution, and then adding NaBH4A solution; measuring absorbance through an ultraviolet spectrophotometer and substituting the absorbance into a standard curve equation; or the method comprises the following steps: soaking the cellulose filter paper into the mixed solution and then airing; dripping NaBH after dripping a water sample to be detected4The solution is subjected to standard colorimetry or absorbance measurement by solid ultraviolet spectrophotometry. The method of the invention does not need to adopt complex and expensive instruments, has a detection result similar to the ICP-MS and other methods, and meets the industrial requirements.
Description
Technical Field
The invention belongs to the technical field of chemical analysis, and particularly relates to a quick and reusable hexavalent chromium ion detection system and method.
Background
Cr (VI) exists in the form of anion, has high chemical activity, small volume and high solubility, is easy to generate harm to animals, plants and human bodies, and is even considered to have carcinogenic effect, so that the selective detection of the high-toxicity chromium (VI) is necessary; although ICP-MS, atomic spectroscopy, etc. techniques have high sensitivity, they cannot be directly used for selective detection of cr (vi); in addition, the existing method can only detect Cr (VI) or remove Cr (VI), and can not effectively realize the removal of Cr (VI) at the same time of detection.
Disclosure of Invention
Aiming at the problems of the existing hexavalent chromium ion detection technology, the invention provides a rapid and reusable hexavalent chromium ion detection system and method, which are characterized in that a methylene blue solution, a gallic acid modified gold nanoparticle solution and NaBH are adopted4The solution forms a detection system, the detection system directly detects a water sample containing Cr (VI), or forms detection filter paper after the water sample is immersed by the filter paper, the Cr (VI) content of the water sample can be rapidly detected on site, and the detection system can be repeatedly used.
One of the hexavalent chromium ion detection systems capable of being rapidly and repeatedly utilized comprises methylene blue solution, gallic acid modified gold nanoparticle solution and NaBH4A solution; wherein the concentration of the methylene blue solution is 20 mu M, the concentration of the gallic acid modified gold nanoparticle solution is 40nM, and the concentration of the sodium borohydride solution is 0.04M; gold nanoparticles modified by gallic acid according to molar ratio in detection system, namely methylene blue NaBH4=1:55556:4444480。
The second quick and reusable hexavalent chromium ion detection system comprises cellulose filter paper, methylene blue solution, gallic acid modified gold nanoparticle solution and NaBH4A solution; wherein the concentration of methylene blue solution is 20 μ M, the concentration of gallic acid modified gold nanoparticle solution is 40nM, and NaBH4The concentration of the solution was 0.04M; gold nanoparticles modified by gallic acid according to molar ratio in detection system, namely methylene blue NaBH4=1:55556:4444480。
The preparation method of the gallic acid modified gold nanoparticle solution comprises the following steps:
1. adding HAuCl4Heating the solution to boiling, adding a sodium citrate solution, continuously heating and stirring for 15min to change the color of the mixed solution from light yellow to red, and then cooling in air to normal temperature to obtain a gold nanoparticle solution modified by sodium citrate; the HAuCl4The concentration of the solution is 0.24 mM, the mass concentration of the sodium citrate solution is 1 percent, and the sodium citrate solution and HAuCl are mixed4The dosage ratio of the solution is 700 mu L to 20 mL;
2. adding gallic acid solution into the gold nanoparticle solution modified by sodium citrate, wherein the concentration of the gallic acid solution is 27mM, and the gallic acid solution and HAuCl4The dosage ratio of the solution is 90 mu L to 20 mL; then stirring for 4h, centrifuging again at the speed of 9300rpm for 15min, and precipitating the materials generated by the reaction in a particle state under the action of high-speed centrifugation;then removing the supernatant, adding water into the solid phase, uniformly stirring, re-dispersing the precipitated particles, and preparing the gallic acid modified gold nanoparticle solution with the concentration of 40 nM.
One of the hexavalent chromium ion detection methods of the present invention is performed according to the following steps:
1. preparing hexavalent chromium standard solutions with different concentrations respectively, and preparing a blank solution at the same time, wherein the concentration of the hexavalent chromium standard solution is 0-100 mu g/L;
2. mixing a methylene blue solution and a gallic acid modified gold nanoparticle solution to form a mixed solution, then respectively adding a blank solution and hexavalent chromium standard solutions with different concentrations into the mixed solution, adding 10 mu L of the blank solution/hexavalent chromium standard solution into 1 mL of the methylene blue solution according to the proportion, and then adding NaBH4Stirring and mixing the solution for reaction for 2min to respectively form mixed standard solutions;
3. measuring the absorbance of each mixed standard solution by using water as a reference solution through a spectrophotometer at the wavelength of 664 nm, drawing a standard curve by using the concentration of hexavalent chromium ions as a horizontal coordinate and the absorbance A as a vertical coordinate, and forming a standard curve equation y = ax + b, wherein y is the absorbance, and x is the concentration of the hexavalent chromium ions of the hexavalent chromium standard solution;
4. adding a water sample to be detected into the mixed solution, adding 10 mu L of the water sample to be detected into 1 mL of methylene blue solution according to the proportion, and then adding NaBH4Stirring and mixing the solution for reaction for 2min to form a solution to be detected;
5. and measuring the absorbance of the solution to be detected by an ultraviolet spectrophotometer at the wavelength of 664 nm, and substituting the absorbance value into a standard curve equation to obtain the concentration of the hexavalent chromium ions of the water sample to be detected.
In the method, when the absorbance value measured in the step 5 exceeds the range of the standard curve equation, the water sample to be detected is diluted and then measured according to the steps 4 and 5 until data which can be calculated by the standard curve equation is obtained, and the concentration of the hexavalent chromium ions of the water sample to be detected is calculated according to the dilution times.
In the method, the solution to be detected is placed in the air for 30min and then returns to the step 4 to be used as the mixed solution, and the water sample to be detected is measured again and can be recycled for more than 10 times.
In the method, the detection limit of the hexavalent chromium ions is 0.061 nanomole, and the linear range is 0.1-100 nanomole.
The second method for detecting hexavalent chromium ions of the invention comprises the following steps:
1. preparing hexavalent chromium standard solutions with different concentrations respectively, and preparing a blank solution at the same time, wherein the concentration of the hexavalent chromium standard solution is between 0.1 and 2.0 mu M;
2. mixing a methylene blue solution and a gallic acid modified gold nanoparticle solution to form a mixed solution; soaking the cellulose filter paper into the mixed solution, taking out and airing to form detection filter paper;
3. respectively dripping the blank solution and the hexavalent chromium standard solution on detection filter paper, and then dripping NaBH4Solution, forming standard filter paper with different colors; wherein the blank solution/hexavalent chromium standard solution and NaBH4The volume ratio of the solution is 1: 2;
4. dropwise adding a water sample to be detected on detection filter paper, and then dropwise adding NaBH4Solution to form a test filter paper; wherein the water sample to be detected and NaBH4The volume ratio of the solution is 1: 2;
5. and comparing the colors of the test filter paper and different standard filter papers, wherein the hexavalent chromium concentration corresponding to the standard filter paper with the same or similar color as the test filter paper is the hexavalent chromium ion concentration of the water sample to be detected.
In the third method, when the color of the filter paper tested in the step 5 is beyond the color range of the standard filter paper, the water sample to be detected is diluted and then measured according to the steps 5 and 6 until the color is similar to that of the standard filter paper, and the concentration of the hexavalent chromium ions of the water sample to be detected is calculated according to the dilution times.
The third method for detecting hexavalent chromium ions comprises the following steps:
1. preparing hexavalent chromium standard solutions with different concentrations respectively, and preparing a blank solution at the same time, wherein the concentration of the hexavalent chromium standard solution is between 0.1 and 2.0 mu M;
2. mixing a methylene blue solution and a gallic acid modified gold nanoparticle solution to form a mixed solution; soaking the cellulose filter paper into the mixed solution, taking out and airing to form detection filter paper;
3. respectively dripping the blank solution and the hexavalent chromium standard solution on detection filter paper, and then dripping NaBH4Solution, forming standard filter paper with different colors; wherein the blank solution/hexavalent chromium standard solution and NaBH4The volume ratio of the solution is 1: 2;
4. taking blank fiber filter paper as a reference, measuring the absorbance of standard filter paper by adopting a solid ultraviolet spectrophotometer at the wavelength of 664 nm, drawing a standard curve by taking the concentration of hexavalent chromium ions as a horizontal coordinate and taking the absorbance A as a vertical coordinate, and forming a standard curve equation y = ax + b, wherein y is the absorbance, and x is the concentration of hexavalent chromium ions in the hexavalent chromium standard solution;
5. dropwise adding a water sample to be detected on detection filter paper, and then dropwise adding NaBH4Solution to form a test filter paper; wherein the water sample to be detected and NaBH4The volume ratio of the solution is 1: 2;
6. and (3) measuring the absorbance of the test filter paper by using a solid ultraviolet spectrophotometer at the wavelength of 664 nm, and substituting the absorbance value into a standard curve equation to obtain the concentration of the hexavalent chromium ions of the water sample to be detected.
In the third method, when the absorbance value measured in the step 6 exceeds the range of the standard curve equation, the water sample to be detected is diluted and then measured according to the steps 5 and 6 until data which can be calculated by the standard curve equation is obtained, and the concentration of the hexavalent chromium ions of the water sample to be detected is calculated according to the dilution times.
In the second method and the third method, the filter paper to be tested is placed in the air for 1 hour, the color is recovered to be blue, namely, the color displayed when the blank solution is detected, then the filter paper is cleaned by hydrochloric acid solution with the weight concentration of 5%, and is dried to form the reusable detection filter paper, and the reusable detection filter paper can be reused for at least 7 times.
In the second and third methods, the detection limit is 0.1 micromolar, and the linear range is 0.1 to 2 micromolar.
The method of the invention does not need to adopt complex and expensive instruments, has a detection result similar to the ICP-MS and other methods, meets the industrial requirements, can be prepared into detection filter paper, and has the advantages of simple preparation, low cost, low detection limit, high selectivity, convenient use and reusability; the test range is wide, the operation of professional personnel is not needed, and the method is particularly suitable for rapidly detecting the content of hexavalent chromium on site.
The method can selectively detect Cr (VI) and is based on a gallic acid modified gold nanoparticle catalysis methylene blue colorimetric signal amplification strategy; the method is simple, high in sensitivity and good in selectivity, can be recycled for multiple times, and has the detection limit of 0.061 nanomole, the linear range of 0.1-100 nanomole, the detection limit of naked eye filter paper of 0.1 micromole and the linear range of 0.1-2 micromole; and (3) performing target colorimetric analysis to modify methylene blue and gold nanoparticles on filter paper, so that the Cr (VI) can be removed while colorimetric detection is realized.
Detailed Description
The methylene blue solution, the gallic acid solution, the sodium citrate solution, the chloroauric acid solution and the NaBH adopted in the embodiment of the invention4The solution was prepared as a commercially available analytical reagent.
The cellulose filter paper used in the examples of the present invention is a commercially available product.
The hydrochloric acid solution adopted in the embodiment of the invention is prepared by a commercially available analytical reagent.
In the embodiment of the invention, the number of hexavalent chromium standard solutions in one of the hexavalent chromium ion detection methods is at least 5, and the concentration difference of hexavalent chromium standard solutions with adjacent concentrations is controlled to be 0-100 mu g/L according to the requirement of measurement accuracy.
In the second method for detecting hexavalent chromium ions in the embodiment of the present invention, the number of the hexavalent chromium standard solutions is at least 5, and the concentration difference of the hexavalent chromium standard solutions with adjacent concentrations is controlled between 0.1 μ M and 2.0 μ M according to the requirement of the measurement accuracy.
The preparation method of the gallic acid modified gold nanoparticle solution in the embodiment of the invention comprises the following steps:
adding HAuCl4Heating the solution to boiling, adding sodium citrate solution, heating and stirring for 15min to change the color of the mixed solution from light yellow to redThen, air-cooling to normal temperature to obtain a gold nanoparticle solution modified by sodium citrate; the HAuCl4The concentration of the solution is 0.24 mM, the mass concentration of the sodium citrate solution is 1 percent, and the sodium citrate solution and HAuCl are mixed4The dosage ratio of the solution is 700 mu L to 20 mL;
adding gallic acid solution into the gold nanoparticle solution modified by sodium citrate, wherein the concentration of the gallic acid solution is 27mM, and the gallic acid solution and HAuCl4The dosage ratio of the solution is 90 mu L to 20 mL; then stirring for 4h, centrifuging again at the speed of 9300rpm for 15min, and precipitating the materials generated by the reaction in a particle state under the action of high-speed centrifugation; then removing the supernatant, adding water into the solid phase, uniformly stirring, re-dispersing the precipitated particles, and preparing the gallic acid modified gold nanoparticle solution with the concentration of 40 nM.
Example 1
The hexavalent chromium ion detection system comprises methylene blue solution, gallic acid modified gold nanoparticle solution and NaBH4A solution; wherein the concentration of the methylene blue solution is 20 mu M, the concentration of the gallic acid modified gold nanoparticle solution is 40nM, and the concentration of the sodium borohydride solution is 0.04M; gold nanoparticles modified by gallic acid according to molar ratio in detection system, namely methylene blue NaBH4=1:55556:4444480；
Respectively adding 1 mL of methylene blue solution and 9 mu L of gallic acid modified gold nanoparticle solution into 6 2 mL centrifuge tubes, respectively adding 10 mu L of 0 mu g/L (blank solution), 50 mu g/L, 100 mu g/L, 200 mu g/L, 300 mu g/L and 500 mu g/L hexavalent chromium standard solutions, and finally adding 40 mu L NaBH4Reacting for 2 min; measuring the absorbance of each solution at 664 nm by using water as a reference solution;
drawing a standard curve by taking the concentration of hexavalent chromium ions as an abscissa and the absorbance A as an ordinate to form a standard curve equation y = ax + b, wherein y is the absorbance, and x is the concentration of the hexavalent chromium ions of the hexavalent chromium standard solution;
mixing 970 mu L of GBW08608 solution (the concentration of metal ions is 12.0 ng/g of Cd ions, 51 ng/g of Pb ions, 51 ng/g of Cu ions, 91 ng/g of Zn ions, 61ng/g of Ni ions and 33 ng/g of Cr ions) with 30 mu L of hexavalent chromium ion solution with the concentration of 1 mg/L, adding 200 mu L of the mixed solution into 2800 mu L of deionized water to prepare a water sample to be detected with the concentration of hexavalent chromium ions of 2 mu g/L for testing accuracy;
adding a water sample to be detected into the mixed solution, adding 10 mu L of the water sample to be detected into 1 mL of methylene blue solution according to the proportion, and then adding NaBH4Stirring and mixing the solution (40 mu L) for reaction for 2min to form a solution to be detected;
measuring the absorbance of the solution to be detected by an ultraviolet spectrophotometer at the wavelength of 664 nm, and substituting the absorbance value into a standard curve equation to obtain the concentration of the hexavalent chromium ions of the water sample to be detected, wherein the concentration of the hexavalent chromium ions is 2 mug/L; and detecting the water sample to be detected by using ICP-MS, wherein the obtained result accords with the mode.
Example 2
Placing the solution to be detected in the embodiment 1 in the air for 30min to serve as a mixed solution, and adding 10 mu L of the water sample to be detected again; the water sample to be detected is as follows: GBW (E) 080082 solution (metal ion concentration is Cd ion 5.00 mug/mL, Pb ion 5.00 mug/mL, Cu ion 5.00 mug/mL, Zn ion 5.00 mug/mL) 998 muL and 2 muL hexavalent chromium standard solution with concentration of 1 mg/L are mixed to prepare mixed solution, the concentration of hexavalent chromium ions is 2 mug/L;
detecting to obtain a water sample to be detected according to the mode of the embodiment 1, wherein the concentration of hexavalent chromium ions is 2 mug/L; repeatedly using the solution to be detected for 10 times, respectively detecting water samples with different hexavalent chromium ion concentrations, and obtaining a result which is consistent with the mode; and detecting the water sample to be detected by using ICP-MS, wherein the obtained result is consistent with each detection result.
Example 3
The rapid and reusable hexavalent chromium ion detection system comprises cellulose filter paper, methylene blue solution, gallic acid modified gold nanoparticle solution and NaBH4A solution; wherein the concentration of methylene blue solution is 20 μ M, the concentration of gallic acid modified gold nanoparticle solution is 40nM, and NaBH4The concentration of the solution was 0.04M; gold nanoparticles modified by gallic acid according to molar ratio in detection system, namely methylene blue NaBH4=1:55556:4444480；
Mixing a methylene blue solution and a gallic acid modified gold nanoparticle solution to form a mixed solution; soaking the cellulose filter paper into the mixed solution, taking out and airing to form detection filter paper;
preparing hexavalent chromium standard solutions with different concentrations respectively, and preparing blank solutions, wherein the concentrations of the hexavalent chromium standard solutions are 0.1 mu M, 0.2 mu M, 0.4 mu M, 0.6 mu M, 0.8 mu M, 1.0 mu M and 2.0 mu M respectively;
respectively dripping the blank solution and each hexavalent chromium standard solution on detection filter paper, and then dripping NaBH4Solution, forming standard filter paper with different colors; wherein the blank solution/hexavalent chromium standard solution and NaBH4The volume ratio of the solution is 1: 2;
uniformly mixing the filtered lake water with a hexavalent chromium standard solution with the concentration of 1 mg/L by adopting the lake water filtered by a filter membrane with the thickness of 0.22 mu M to prepare a water sample to be detected, wherein the concentration of the hexavalent chromium ions is 0.2 mu M;
dropwise adding a water sample to be detected on detection filter paper, and then dropwise adding NaBH4Solution to form a test filter paper; wherein the water sample to be detected and NaBH4The volume ratio of the solution is 1: 2;
comparing the colors of the test filter paper and different standard filter papers, wherein the hexavalent chromium concentration corresponding to the standard filter paper with the same or similar color as the test filter paper is the hexavalent chromium ion concentration of the water sample to be detected, namely 0.2 mu M; and detecting the water sample to be detected by using ICP-MS, wherein the obtained result accords with the mode.
Example 4
The method is the same as the embodiment 3, and is different from the following steps:
after obtaining the standard filter paper, measuring the absorbance of the standard filter paper by using a solid ultraviolet spectrophotometer at the wavelength of 664 nm, drawing a standard curve by taking the concentration of hexavalent chromium ions as an abscissa and the absorbance A as an ordinate, and forming a standard curve equation y = ax + b, wherein y is the absorbance and x is the concentration of the hexavalent chromium ions in the hexavalent chromium standard solution;
adopting tap water filtered by a filter membrane of 0.22 mu m, and uniformly mixing the filtered tap water with a hexavalent chromium solution with the concentration of 1 mg/L; preparing a water sample to be detected with the concentration of hexavalent chromium ions being 0.4 mu M;
dropwise adding a water sample to be detected on detection filter paper, and then dropwise adding NaBH4Solution to form a test filter paper; wherein the water sample to be detected and NaBH4The volume ratio of the solution is 1: 2;
measuring the absorbance of the test filter paper by using a solid ultraviolet spectrophotometer under the wavelength of 664 nm, and substituting the absorbance value into a standard curve equation to obtain the concentration of hexavalent chromium ions of the water sample to be detected, wherein the concentration of the hexavalent chromium ions is 0.4 mu M; and detecting the water sample to be detected by using ICP-MS, wherein the obtained result accords with the mode.
Example 5
Placing the filter paper to be tested in the embodiment 3 in the air for 1h, recovering the color to be blue, washing the filter paper by using a hydrochloric acid solution with the weight concentration of 5%, and airing to form the reusable detection filter paper;
adopting spring water filtered by a filter membrane of 0.22 mu m, and uniformly mixing the filtered spring water with a hexavalent chromium solution with the concentration of 1 mg/L; preparing a water sample to be detected with the concentration of hexavalent chromium ions being 0.1 mu M;
obtaining the concentration of hexavalent chromium ions of the water sample to be detected to be 0.1 mu M according to the mode of the embodiment 3; the solution to be detected is repeatedly used for 6 times, water samples with different hexavalent chromium ion concentrations are respectively detected, and the obtained result conforms to the mode; and detecting the water sample to be detected by using ICP-MS, wherein the obtained result is consistent with each detection result.
Example 6
Placing the filter paper to be tested in the embodiment 4 in the air for 1h, recovering the color to be blue, washing the filter paper by using a hydrochloric acid solution with the weight concentration of 5%, and airing to form the reusable detection filter paper;
adopting spring water filtered by a filter membrane of 0.22 mu m, and uniformly mixing the filtered spring water with a hexavalent chromium solution with the concentration of 1 mg/L; preparing a water sample to be detected with the concentration of hexavalent chromium ions being 0.4 mu M;
obtaining the concentration of hexavalent chromium ions of the water sample to be detected to be 0.4 mu M in the way of the embodiment 4; the solution to be detected is repeatedly used for 6 times, water samples with different hexavalent chromium ion concentrations are respectively detected, and the obtained result conforms to the mode; and detecting the water sample to be detected by using ICP-MS, wherein the obtained result is consistent with each detection result.
Claims (3)
1. A quick and reusable hexavalent chromium ion detection method is characterized in that a quick and reusable hexavalent chromium ion detection system is adopted, and the system comprises methylene blue solution, gallic acid modified gold nanoparticle solution and NaBH4A solution; wherein the concentration of the methylene blue solution is 20 mu M, the concentration of the gallic acid modified gold nanoparticle solution is 40nM, and the concentration of the sodium borohydride solution is 0.04M; gold nanoparticles modified by gallic acid according to molar ratio in detection system, namely methylene blue NaBH4=1:55556:4444480；
The preparation method of the gallic acid modified gold nanoparticle solution comprises the following steps:
(1) adding HAuCl4Heating the solution to boiling, adding a sodium citrate solution, continuously heating and stirring for 15min to change the color of the mixed solution from light yellow to red, and then cooling in air to normal temperature to obtain a gold nanoparticle solution modified by sodium citrate; the HAuCl4The concentration of the solution is 0.24 mM, the mass concentration of the sodium citrate solution is 1 percent, and the sodium citrate solution and HAuCl are added4The dosage ratio of the solution is 700 mu L to 20 mL;
(2) adding gallic acid solution into the gold nanoparticle solution modified by sodium citrate, wherein the concentration of the gallic acid solution is 27mM, and the gallic acid solution and HAuCl4The dosage ratio of the solution is 90 mu L to 20 mL; then stirring for 4h, centrifuging again at the speed of 9300rpm for 15min, and precipitating the materials generated by the reaction in a particle state under the action of high-speed centrifugation; then removing the supernatant, adding water into the solid phase, uniformly stirring, re-dissolving and dispersing the precipitated particles, and preparing gallic acid modified gold nanoparticle solution with the concentration of 40 nM;
the detection method comprises the following steps:
(1) preparing hexavalent chromium standard solutions with different concentrations respectively, and preparing a blank solution at the same time, wherein the concentration of the hexavalent chromium standard solution is 0-100 mu g/L;
(2) mixing methylene blue solution and gallic acid modified gold nanoparticle solutionForming a mixed solution, respectively adding a blank solution and hexavalent chromium standard solutions with different concentrations into the mixed solution, adding 10 mu L of the blank solution/hexavalent chromium standard solution into 1 mL of methylene blue solution according to the proportion, and then adding NaBH4Stirring and mixing the solution for reaction for 2min to respectively form mixed standard solutions;
(3) measuring the absorbance of each mixed standard solution by using water as a reference solution through a spectrophotometer at the wavelength of 664 nm, drawing a standard curve by using the concentration of hexavalent chromium ions as a horizontal coordinate and the absorbance A as a vertical coordinate, and forming a standard curve equation y = ax + b, wherein y is the absorbance, and x is the concentration of the hexavalent chromium ions of the hexavalent chromium standard solution;
(4) adding a water sample to be detected into the mixed solution, adding 10 mu L of the water sample to be detected into 1 mL of methylene blue solution according to the proportion, and then adding NaBH4Stirring and mixing the solution for reaction for 2min to form a solution to be detected;
(5) measuring the absorbance of the solution to be detected by an ultraviolet spectrophotometer at the wavelength of 664 nm, and substituting the absorbance value into a standard curve equation to obtain the concentration of hexavalent chromium ions of the water sample to be detected;
after the detection method is completed, the solution to be detected in the step (5) is placed in the air for 30min and then returns to the step (4) to be used as a mixed solution, and the water sample to be detected is measured again, so that the mixed solution can be reused for at least 10 times.
2. A quick and reusable hexavalent chromium ion detection method is characterized in that a quick and reusable hexavalent chromium ion detection system is adopted, and the system comprises cellulose filter paper, methylene blue solution, gallic acid modified gold nanoparticle solution and NaBH4A solution; wherein the concentration of methylene blue solution is 20 μ M, the concentration of gallic acid modified gold nanoparticle solution is 40nM, and NaBH4The concentration of the solution was 0.04M; gold nanoparticles modified by gallic acid according to molar ratio in detection system, namely methylene blue NaBH4=1:55556:4444480；
The preparation method of the gallic acid modified gold nanoparticle solution comprises the following steps:
(1) adding HAuCl4Heating the solution to boiling, adding a sodium citrate solution, continuously heating and stirring for 15min to change the color of the mixed solution from light yellow to red, and then cooling in air to normal temperature to obtain a gold nanoparticle solution modified by sodium citrate; the HAuCl4The concentration of the solution is 0.24 mM, the mass concentration of the sodium citrate solution is 1 percent, and the sodium citrate solution and HAuCl are added4The dosage ratio of the solution is 700 mu L to 20 mL;
(2) adding gallic acid solution into the gold nanoparticle solution modified by sodium citrate, wherein the concentration of the gallic acid solution is 27mM, and the gallic acid solution and HAuCl4The dosage ratio of the solution is 90 mu L to 20 mL; then stirring for 4h, centrifuging again at the speed of 9300rpm for 15min, and precipitating the materials generated by the reaction in a particle state under the action of high-speed centrifugation; then removing the supernatant, adding water into the solid phase, uniformly stirring, re-dissolving and dispersing the precipitated particles, and preparing gallic acid modified gold nanoparticle solution with the concentration of 40 nM;
the detection method comprises the following steps:
(1) preparing hexavalent chromium standard solutions with different concentrations respectively, and preparing a blank solution at the same time, wherein the concentration of the hexavalent chromium standard solution is between 0.1 and 2.0 mu M;
(2) mixing a methylene blue solution and a gallic acid modified gold nanoparticle solution to form a mixed solution; soaking the cellulose filter paper into the mixed solution, taking out and airing to form detection filter paper;
(3) respectively dripping the blank solution and the hexavalent chromium standard solution on detection filter paper, and then dripping NaBH4Solution, forming standard filter paper with different colors; wherein the blank solution/hexavalent chromium standard solution and NaBH4The volume ratio of the solution is 1: 2;
(4) dropwise adding a water sample to be detected on detection filter paper, and then dropwise adding NaBH4Solution to form a test filter paper; wherein the water sample to be detected and NaBH4The volume ratio of the solution is 1: 2;
(5) comparing the colors of the test filter paper and different standard filter papers, wherein the hexavalent chromium concentration corresponding to the standard filter paper with the same or similar color as the test filter paper is the hexavalent chromium ion concentration of the water sample to be detected;
and (3) after the detection method is completed, placing the test filter paper in the step (5) in the air for 1h, recovering the color to blue, namely, the color displayed when the blank solution is detected, then washing the filter paper by using a hydrochloric acid solution with the weight concentration of 5%, airing to form the reusable detection filter paper, and returning to the step (3) for reuse, so that the reusable detection filter paper can be reused for at least 7 times.
3. A quick and reusable hexavalent chromium ion detection method is characterized in that a quick and reusable hexavalent chromium ion detection system is adopted, and the system comprises cellulose filter paper, methylene blue solution, gallic acid modified gold nanoparticle solution and NaBH4A solution; wherein the concentration of methylene blue solution is 20 μ M, the concentration of gallic acid modified gold nanoparticle solution is 40nM, and NaBH4The concentration of the solution was 0.04M; gold nanoparticles modified by gallic acid according to molar ratio in detection system, namely methylene blue NaBH4=1:55556:4444480；
The preparation method of the gallic acid modified gold nanoparticle solution comprises the following steps:
(1) adding HAuCl4Heating the solution to boiling, adding a sodium citrate solution, continuously heating and stirring for 15min to change the color of the mixed solution from light yellow to red, and then cooling in air to normal temperature to obtain a gold nanoparticle solution modified by sodium citrate; the HAuCl4The concentration of the solution is 0.24 mM, the mass concentration of the sodium citrate solution is 1 percent, and the sodium citrate solution and HAuCl are added4The dosage ratio of the solution is 700 mu L to 20 mL;
(2) adding gallic acid solution into the gold nanoparticle solution modified by sodium citrate, wherein the concentration of the gallic acid solution is 27mM, and the gallic acid solution and HAuCl4The dosage ratio of the solution is 90 mu L to 20 mL; then stirring for 4h, centrifuging again at the speed of 9300rpm for 15min, and precipitating the materials generated by the reaction in a particle state under the action of high-speed centrifugation; then the supernatant liquid is removed, and the supernatant liquid is removed,adding water into the solid phase, uniformly stirring, and re-dissolving and dispersing the precipitated particles to prepare a gallic acid modified gold nanoparticle solution with the concentration of 40 nM;
the detection method comprises the following steps:
(1) preparing hexavalent chromium standard solutions with different concentrations respectively, and preparing a blank solution at the same time, wherein the concentration of the hexavalent chromium standard solution is between 0.1 and 2.0 mu M;
(2) mixing a methylene blue solution and a gallic acid modified gold nanoparticle solution to form a mixed solution; soaking the cellulose filter paper into the mixed solution, taking out and airing to form detection filter paper;
(3) respectively dripping the blank solution and the hexavalent chromium standard solution on detection filter paper, and then dripping NaBH4Solution, forming standard filter paper with different colors; wherein the blank solution/hexavalent chromium standard solution and NaBH4The volume ratio of the solution is 1: 2;
(4) measuring the absorbance of the standard filter paper by using a solid ultraviolet spectrophotometer at a wavelength of 664 nm, drawing a standard curve by taking the concentration of hexavalent chromium ions as an abscissa and the absorbance A as an ordinate, and forming a standard curve equation y = ax + b, wherein y is the absorbance, and x is the concentration of the hexavalent chromium ions in the hexavalent chromium standard solution;
(5) dropwise adding a water sample to be detected on detection filter paper, and then dropwise adding NaBH4Solution to form a test filter paper; wherein the water sample to be detected and NaBH4The volume ratio of the solution is 1: 2;
(6) measuring the absorbance of the test filter paper by using a solid ultraviolet spectrophotometer under the wavelength of 664 nm, and substituting the absorbance value into a standard curve equation to obtain the concentration of hexavalent chromium ions of the water sample to be detected;
and (3) after the detection method is completed, placing the test filter paper in the step (6) in the air for 1h, recovering the color to blue, namely, the color displayed when the blank solution is detected, then washing the filter paper by using a hydrochloric acid solution with the weight concentration of 5%, airing to form the reusable detection filter paper, and returning to the step (3) for reuse, so that the reusable detection filter paper can be reused for at least 7 times.
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