CN113125407B - Cr (chromium)6+Ion rapid detection method - Google Patents
Cr (chromium)6+Ion rapid detection method Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 31
- 239000011651 chromium Substances 0.000 title description 39
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title description 10
- 229910052804 chromium Inorganic materials 0.000 title description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 17
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- CBMPTFJVXNIWHP-UHFFFAOYSA-L disodium;hydrogen phosphate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].OP([O-])([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O CBMPTFJVXNIWHP-UHFFFAOYSA-L 0.000 claims description 9
- 239000008055 phosphate buffer solution Substances 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
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- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000010931 gold Substances 0.000 abstract description 22
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 229910000497 Amalgam Inorganic materials 0.000 abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052737 gold Inorganic materials 0.000 abstract description 3
- 229910021389 graphene Inorganic materials 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 3
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- 230000015572 biosynthetic process Effects 0.000 description 5
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- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
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- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
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- 239000000872 buffer Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 208000001780 epistaxis Diseases 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
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- 239000010985 leather Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 210000004400 mucous membrane Anatomy 0.000 description 1
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- 239000013589 supplement Substances 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 231100000397 ulcer Toxicity 0.000 description 1
Classifications
-
- 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
- G01N21/62—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
- G01N21/65—Raman scattering
-
- 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
- G01N21/62—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
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The invention belongs to the technical field of heavy metal detection, and discloses a Cr 6+ ion rapid detection method, which comprises the following steps: s1, modifying a dendritic Au@Pd nano material to the surface of mercapto-functionalized graphene (GO-SH), and marking the obtained product as GO/Au@Pd; s2, further reacting the GO/Au@Pd synthesized in the step S1 with Hg 2+ to form amalgam, and marking the obtained product as GO/Au-Hg@Pd-Hg; s3, mixing the GO/Au-Hg@Pd-Hg synthesized in the step S2 with TMB and Cr 6+ in deionized water, detecting the intensity change value of a Raman peak of the mixed solution at a position of 1608cm ‑1, and calculating the concentration of Cr 6+ in the sample to be detected according to a quantitative analysis standard working curve. In the method, GO/Au-Hg@Pd-Hg serves as a catalyst, so that the catalyst has good dispersibility and stability, gold amalgam and palladium amalgam in the catalyst can cooperatively catalyze TMB, and dendritic nano gold can monitor the Raman signal of a TMB oxidation product in situ, so that the method has the advantages of mild reaction condition, safety, environmental protection and high detection sensitivity, and is very suitable for rapid and high-sensitivity detection of Cr 6+ ions on a base layer and on site.
Description
Technical Field
The invention relates to the technical field of heavy metal detection, in particular to a rapid detection method for Cr 6+ ions.
Background
With the acceleration of the progress of human industrialization, a large amount of heavy metal ions are continuously released into the environment. Chromium is a common heavy metal element, and mainly appears in three forms of metallic chromium (Cr), trivalent chromium (Cr 3+) and hexavalent chromium (Cr 6+) in nature. It was found that Cr 6+ was the most detrimental to occupational health in the three forms above due to its relatively stronger fluidity and carcinogenic properties. It can invade human body through alimentary canal, respiratory tract, skin and mucous membrane to make lung and nasal cavity etc. become cancerous. In addition, cr 6+ causes many other health problems, such as inhalation of certain higher concentrations of Cr 6+ causes runny nose, sneezing, itching, epistaxis, ulcers and perforation of the nasal septum. Therefore, it is highly necessary to detect and monitor the chromium content in samples such as environmental water. Today, many countries have strict restrictions on the chromium content of environmental water, for example the united states environmental protection agency clearly states that the total chromium content in water cannot exceed 100ppb; the European Union specifies that the chromium content in export leather should not exceed 3ppm.
Common detection methods of Cr 6+ mainly include mass spectrometry, ion chromatography, atomic absorption spectrometry, spectrophotometry and the like. The former 3 methods, although having high sensitivity and good accuracy, all require large and expensive instruments and professional operators, and have high detection cost and long time consumption; while spectrophotometry, although simple to operate, has a lower sensitivity. Therefore, it is very necessary to develop a novel rapid, simple, low-cost and high-sensitivity Cr 6+ detection method, so that the on-site, rapid and high-sensitivity detection of Cr 6+ can be realized, and further powerful technical supplements are provided for effectively monitoring the quality of drinking water, reducing the danger of industrial wastewater and the like.
Disclosure of Invention
In order to solve the technical defects, the invention develops a rapid, simple and high-sensitivity on-site Cr 6+ ion detection method based on the in-situ high-efficiency catalysis of the difunctional GO/Au-Hg@Pd-Hg nano material to TMB in the presence of Cr 6+.
A Cr 6+ ion rapid detection method comprises the following steps:
S1, wrapping Pd nano particles with the particle size within 1-10nm on the surface of dendritic nano Au by adopting an ascorbic acid reduction method at room temperature, and marking the obtained product as a dendritic Au@Pd nano material;
Preferably, in the step S1, the particle size of the dendritic nano Au is 40-60 nm, and the particle size of the dendritic au@pd nanomaterial is 42-80 nm, which has both raman activity and catalytic activity.
S2, forming Au-S, pd-S on the surface of GO-SH (mercapto graphene) to modify the dendritic Au@Pd nano material synthesized in the step S1, centrifugally washing the obtained product by using deionized water, and then re-suspending the product into an equal volume of citric acid-disodium hydrogen phosphate buffer solution, wherein the obtained product is GO/Au@Pd;
Preferably, the preparation method of GO-SH in the step S2 specifically comprises the following steps: firstly, a certain amount of GO (graphene oxide) is ultrasonically dispersed into ethanol solution, then a certain amount of EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) is added into the ethanol solution, the mixture is stirred for 12 to 24 hours at room temperature, and then a certain volume of AET (2-aminoethanethiol) solution is added into the mixture to be continuously stirred for 4 to 6 hours. Finally, the mixture is centrifugally washed by deionized water and resuspended in equal volume.
Preferably, the AET solution has a concentration of 1mM; the concentration of the citric acid-disodium hydrogen phosphate buffer solution is 5-25 mM, and the pH value is 4-6.
S3, in a citric acid-disodium hydrogen phosphate buffer system, stirring the GO/Au@Pd obtained in the step S2 and a solution containing Hg 2+ at room temperature for 20-30 min, and centrifuging and re-suspending the mixture into an equal volume of deionized water, wherein the obtained product is GO/Au-Hg@Pd-Hg;
preferably, the formation of GO/Au-Hg@Pd-Hg in step S3 must be carried out in a citric acid-disodium hydrogen phosphate buffer solution having a concentration of 5 to 25mM and a pH of 4 to 6.
Preferably, the concentration of Hg 2+ solution in step S3 is 1mM.
S4, sequentially mixing the product obtained in the step S3 with deionized water, TMB and Cr 6+ to form a catalytic reaction system, reacting for 1-2min, taking part of mixed liquid drops to tinfoil paper, carrying out Raman test by means of a portable Raman spectrometer, taking the concentration of Cr 6+ as an abscissa and the intensity change value of a Raman peak of a TMB oxidation product at a position corresponding to 1608cm -1 as an ordinate, and drawing a quantitative analysis standard working curve;
preferably, the TMB concentration in step S4 is 10mM.
Preferably, the raman test conditions in step S4 are: the laser wavelength was 785nm and the exposure time was 10s, measured 3-5 times on average.
S5, after the Cr 6+ sample with unknown concentration to be detected is preprocessed according to national standard requirements before detection, the intensity change value of the corresponding Raman peak at 1608cm -1 is detected by adopting the method described in the step S4, and according to the working curve described in the step S4 and the limit of Cr 6+ in the national standard, the concentration of Cr 6+ in the sample to be detected can be calculated, and whether the chromium content in the sample to be detected exceeds the standard can be judged.
The invention provides a Cr 6+ rapid detection method, which has the advantages that:
(1) The GO/Au@Pd nano material provided by the invention has the advantages of good stability, good dispersibility, and excellent SERS enhancement activity and catalytic activity. Gold amalgam and palladium amalgam formed by the action of mercury are nontoxic, have good synergistic catalysis effect on TMB, and can greatly improve the detection sensitivity;
(2) Cr 6+ has excellent oxidizing ability, under the catalytic action of GO/Au-Hg@Pd-Hg nano-material, TMB can be rapidly oxidized without adding H 2O2 in a deionized water system, so that the use of an acidic buffer reagent and an unstable reagent is avoided, and the environmental protection, safety and stability of the detection method are improved.
(3) The detection method provided by the invention does not need to depend on a large instrument and professional operators in the use process, the whole process is very simple and quick, and the Raman detection can be carried out by simply centrifuging or filtering an environmental water sample and then mixing the environmental water sample with GO/Au-Hg@Pd-Hg and TMB with a certain concentration for 1-2 min; meanwhile, the catalytic activity of the amalgam formed in the GO/Au-Hg@Pd-Hg nano-material is greatly improved compared with that of the GO/Au@Pd nano-material, so that the detection sensitivity is further improved. In summary, the method is expected to be widely used for on-site, rapid and high-sensitivity detection of the chromium content in samples such as basic-level environmental water.
Detailed Description
The invention will now be further described with reference to examples, which are not intended to limit the scope of the invention but are merely illustrative.
1. Preparation of GO/Au-Hg@Pd-Hg nano material
(1) Synthesis of dendritic nano Au
After 200. Mu.L of 1.0mM HAuCl 4 solution was mixed with 20mL of deionized water, 60. Mu.L of 10mM AgNO 3 solution was added, after thorough mixing, 80. Mu.L of 100mM ascorbic acid was rapidly added, and after 20s of vigorous stirring at room temperature, the mixture was washed by centrifugation with deionized water 2 to 3 times and finally resuspended in deionized water at equal volumes.
(2) Synthesis of dendritic Au@Pd nano material
100. Mu.L of 10mM H 2PdCl6 solution was added to 10mL of the branched nano Au synthesized in step (1) under vigorous stirring at room temperature, and after thoroughly mixing, 40. Mu.L of 100mM ascorbic acid was further added. At this time, the color of the solution was changed from blue to gray black. After stirring for 1h at room temperature, the product was washed by centrifugation with deionized water 2 to 3 times and finally resuspended in deionized water at equal volumes.
(3) Synthesis of GO/Au@Pd nanomaterial
Firstly, dispersing 100mg of GO into 50mL of absolute ethyl alcohol by ultrasonic; then adding 1.9mg of EDC into the mixture, and stirring the mixture at room temperature for 12 hours to ensure that the carboxyl on the surface of GO is activated; then, 50mL of 1mM AET solution was added and stirring was continued for 4 hours, after which the product was centrifuged with deionized water and resuspended in equal volume. This product was designated GO-SH.
Next, 5mL of the dendritic Au@Pd solution synthesized in step (2) was added to 1mL of GO-SH solution, stirred at room temperature for 2 hours, and then centrifugally washed 2 to 3 times with deionized water, and finally resuspended in an equal volume of 10mM citric acid-disodium hydrogen phosphate buffer solution (pH 5), and the obtained product was designated as GO/Au@Pd.
(4) Synthesis of GO/Au-Hg@Pd-Hg
Taking 1mL of the GO/Au@Pd solution synthesized in the step (3), adding 10 mu L of 1mM Hg 2+ solution into the solution, stirring the solution gently at room temperature for 20-30 min, centrifugally washing the solution for 2-3 times by using deionized water, and finally, re-suspending the solution in an equal volume, wherein the obtained product is GO/Au-Hg@Pd-Hg.
The nano material obtained by the above is tested, and the dendritic nano Au prepared by the steps has the particle size of about 50nm; after further coating Pd nano particles, the particle size is increased to about 60 nm; after the amalgam is formed, the grain diameter change is not obvious, and the shape is still in a dendritic structure.
2. Rapid detection process of Cr 6+
20 Mu L of Cr 6+ standard solution with different concentrations is added into a mixed solution of 30 mu L of GO/Au-Hg@Pd-Hg, 30 mu L of deionized water and 20 mu L of 10mM TMB, and after reacting for 1-2min at room temperature, 10 mu L of the mixed solution is dripped onto tinfoil paper for Raman test. The test conditions were: the laser wavelength was 785nm and the exposure time was 10s, measured 5 times on average. Finally, a quantitative analysis standard working curve is drawn by taking the concentration of Cr 6+ as an abscissa and the intensity change value of a Raman peak of a TMB oxidation product at a position of 1608cm -1 as an ordinate. From the standard working curve, it can be seen that the detectable Cr 6+ concentration is as low as 0.01nM.
Examples 1 to 6
Test of Cr 6+ analog samples
First, industrial wastewater and Dongfu water (15000 rpm,5 min) were centrifuged to remove impurities. Next, 100, 400 and 800nM Cr 6+ standard solutions, respectively, were added thereto and left for the test as in examples 1-6, respectively, and after thoroughly mixing, cr 6+ was detected by the method described above. The concentration and recovery rate of Cr 6+ in the simulated sample were estimated from the standard working curve obtained by the above method by measuring the variation of the Raman peak intensity at 1608cm -1 as shown in Table 1 below. From the results, the recovery rates of the three groups of industrial wastewater and the three groups of eastern lake water simulation samples in the implementation methods 1-6 are between 96% and 105%, and the results show that the method has good feasibility in actual sample detection.
Table 1 Cr 6+ simulation sample test results
While the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that the foregoing embodiments are merely illustrative of the invention and not limiting thereof: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The rapid detection method for Cr 6+ ions is characterized by comprising the following steps:
s1, wrapping Pd nano particles with the particle size within 1-10 nm on the surface of dendritic nano Au by adopting an ascorbic acid reduction method at room temperature, and marking the obtained product as a dendritic Au@Pd nano material;
S2, modifying the dendritic Au@Pd nano material synthesized in the step S1 on the surface of the GO-SH by forming Au-S, pd-S, centrifugally washing the obtained product by using deionized water, and then re-suspending the product into an equal volume of citric acid-disodium hydrogen phosphate buffer solution, wherein the obtained product is marked as GO/Au@Pd;
S3, in a citric acid-disodium hydrogen phosphate buffer system, stirring the GO/Au@Pd obtained in the step S2 and a solution containing Hg 2+ at room temperature for 20-30 min, and centrifuging and re-suspending the mixture into an equal volume of deionized water, wherein the obtained product is GO/Au-Hg@Pd-Hg;
S4, mixing the product obtained in the step S3 with deionized water, TMB and Cr 6+ in sequence to form a catalytic reaction system, reacting for 1-2min, taking part of mixed liquid drops to tinfoil paper, carrying out Raman test by means of a portable Raman spectrometer, taking the concentration of Cr 6+ as an abscissa and the intensity variation value of a Raman peak of a TMB oxidation product at a position corresponding to 1608cm -1 as an ordinate, and drawing a quantitative analysis standard working curve;
s5, centrifuging a Cr 6+ sample with unknown concentration to be detected, removing impurities, detecting the intensity change value of a Raman peak at a position of 1608cm -1 corresponding to the sample by adopting the method described in the step S4, calculating the concentration of Cr 6+ in the sample to be detected and judging whether the content of Cr 6+ in the sample exceeds the standard according to the working curve and the national standard limit described in the step S4.
2. The rapid detection method of Cr 6+ ions according to claim 1, wherein the preparation method of the dendritic au@pd nanomaterial is as follows: firstly, using AgNO 3 as a structure guiding agent, synthesizing dendritic nano Au with the particle size of 40-60 nm by an ascorbic acid reduction method at room temperature; then, the nano Au particles with the particle size of 1-10 nm are wrapped on the surface of the dendritic nano Au particles by taking the nano Au particles as seed crystals and further reducing the ascorbic acid.
3. The rapid detection method of Cr 6+ ions according to claim 1, wherein the dendritic Au@Pd nanomaterial in the step S1 is in a dendritic structure and has a particle size of 42-80 nm.
4. The rapid detection method of Cr 6+ ions according to claim 1, wherein the preparation method of GO-SH in step S2 is as follows: firstly, dispersing a certain amount of GO into ethanol solution by ultrasonic, then adding a certain amount of EDC into the ethanol solution, stirring the mixture for 12 to 24 hours at room temperature, adding a certain volume of AET solution, continuously stirring the mixture for 4 to 6 hours, and finally, centrifugally washing the mixture by deionized water, and re-suspending the mixture in an equal volume.
5. The rapid detection method of Cr 6+ ions according to claim 1, wherein the concentration of the citric acid-disodium hydrogen phosphate buffer solution in the step S2 is 5-25 mm, and the ph is 4-6.
6. The rapid detection method of Cr 6+ ions according to claim 1, wherein the reaction of GO/au@pd with Hg 2+ in step S3 is performed in a citric acid-disodium hydrogen phosphate buffer solution having a concentration of 5-25 mm and a ph of 4-6.
7. The rapid detection method of Cr 6+ ions according to claim 1, wherein the raman test conditions in step S4 and step S5 are: the laser wavelength was 785nm and the exposure time was 10s, measured 3-5 times on average.
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