CN104610964A - Preparation method of wavelength adjustable fluorescent carbon dot and application of fluorescent carbon dot in mercury ion detection - Google Patents
Preparation method of wavelength adjustable fluorescent carbon dot and application of fluorescent carbon dot in mercury ion detection Download PDFInfo
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- CN104610964A CN104610964A CN201510009202.7A CN201510009202A CN104610964A CN 104610964 A CN104610964 A CN 104610964A CN 201510009202 A CN201510009202 A CN 201510009202A CN 104610964 A CN104610964 A CN 104610964A
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Abstract
The invention relates to a preparation method of a wavelength adjustable fluorescent carbon dot and an application of the fluorescent carbon dot in mercury ion detection and belongs to the technical field of nanomaterials. The method takes valine as a raw material and obtains a carbon dot aqueous solution with long wavelength and an adjustable fluorescence color by a hydrothermal synthesis method. The method only requires phosphoric acid for adjustment, raw materials are easy to obtain and nontoxic; special protection is not required in a production process; reaction conditions are easy to control; and the obtained carbon dot has the advantages of high productivity, high quantum efficiency, good result repeatability and the like. The method has the characteristics that the method has high productivity and low cost and facilitates mass production, and a preparation technology is simple and the like. The carbon dot prepared by the method can be used for high selectivity and high sensitivity detection of mercury ions, and a limit of detection reaches 1.5*10<-9>Mol/L.
Description
Technical field
The present invention relates to a kind of preparation method of Wavelength tunable fluorescent carbon point and the application in mercury ion detecting thereof, belong to technical field of nano material.
Background technology
Mercury ion is one of heavy metal ion that toxicity is the strongest, is regarded as one of the most general and the most dangerous pollutent of human health and environment.It is revealed, contact high density mercury ion can bring out serious toxic action to human health, as brain injury, central nervous system damage, endocrine system infringement and various cognition and dyskinesia etc.Therefore, need exploitation to have highly selective and sensitivity to mercury ion, and simple and efficient detection method.So far, the method for mercury ion detecting mainly comprises Atomic Absorption Spectroscopy AAS, atomic fluorescence spectroscopy, inductivity coupled plasma mass spectrometry, selectivity cold-atomic fluorescence spectrometry and electrochemical process etc.But these methods need complicated Sample Preparation Procedure and accurate instrument, which greatly limits their practical applications in conventional mercury ion detecting.Therefore, develop mercury ion highly sensitive in water, the simple and efficient detection method of highly selective remains a huge challenge.In order to address these problems, various chemical sensor, as fluorescent optical sensor etc. has been developed, and for mercury ion detecting.Fluorescent carbon point is a kind of New Type of Carbon nanoparticle occurred recent years, the feature such as to stablize have important application prospect because of good water solubility, toxicity extremely low and photoluminescent property in bio-imaging and metal ion detection.The synthetic method of carbon point mainly comprises nitric acid oxidation method, Electrochemical preparation method, pyrolysis method, laser ablation preparation method, template, Microwave-assisted synthesis method etc.But, the blue-fluorescence that the most of excitation wavelength of carbon point of being synthesized by these methods is very short, and the longer green of wavelength or yellow fluorescence carbon point report are seldom, and quantum yield is very low.
Summary of the invention
The object of the invention is to propose a kind of preparation method of Wavelength tunable fluorescent carbon point and the application in mercury ion detecting thereof, to simplify the preparation technology of Wavelength tunable fluorescent carbon point, reduce preparation cost, and make the carbon of preparation point can be used for detecting mercury ion, improve sensitivity and the selectivity of mercury ion detecting, Concentration Testing limit reaches 1.5 × 10
-9mol/L.
The preparation method of the Wavelength tunable fluorescent carbon point that the present invention proposes, comprises the following steps:
(1) added in 10 ml waters by α-amino-isovaleric acid, the mass percent concentration making α-amino-isovaleric acid is 0.2% ~ 30%, is placed on magnetic stirring apparatus, stirs and α-amino-isovaleric acid is fully dissolved, obtain valine aqueous solution;
(2) by the strong phosphoric acid of 1 ~ 10 milliliter, join in the valine aqueous solution of step (1), continue to be stirred to the solution that solution is homogeneous dispersion;
(3) solution of the homogeneous dispersion of step (2) is put into hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, temperature of reaction is 100 DEG C ~ 120 DEG C, and the reaction times is 2 ~ 24 hours, obtains crude product;
(4) or by the solution of the homogeneous dispersion of step (2) put into water bath with thermostatic control, be placed in stirring reaction on magnetic stirring apparatus, temperature of reaction is 60 DEG C ~ 100 DEG C, and the reaction times is 4 ~ 24 hours, obtains crude product;
(5) by the crude product concentration of step (3) or (4) be in 1 mole of often liter of sodium hydroxide solution and after, by the millipore filtration of 0.22 micron, by precipitation removing, obtain blueness, yellow or the green fluorescence carbon point aqueous solution.
The application of Wavelength tunable fluorescent carbon point in mercury ion detecting prepared by the inventive method, comprises the following steps:
(1) concentration of milligram every milliliter, fluorescent carbon point solution dilution to 1 ~ 5 of being prepared by such as claim 1;
(2) on average join in 9 centrifuge tubes by the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters, respectively to adding 2.5 milliliters in 9 centrifuge tubes, volumetric molar concentration is 5 × 10
-3the sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper, calcium, mercury ion solution, and concussion mixes; Get the fluorescent carbon point solution of dilution and the deionized water of 2.5 milliliters in the step (1) that a centrifuge tube adds 2.5 milliliters in addition, as blank group;
(3) after the fluorescent carbon point solution left standstill being added with metal ion step (2) obtained 5 minutes, spectrophotofluorometer is used to detect the fluorescence intensity of mixing solutions, and contrast with blank group, experimental result shows, the fluorescence intensity cancellation adding the carbon point solution of mercury ion is the most obvious, is added with the carbon point solution fluorescence intensity of other metal ions without considerable change;
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is on average joined in 20 centrifuge tubes, in 20 centrifuge tubes, add 2.5 milliliters respectively, concentration is respectively 0 × 10
-9mol/L, 1 × 10
-9mol/L, 2 × 10
-9mol/L, 5 × 10
-9mol/L, 10 × 10
-9mol/L, 20 × 10
-9mol/L, 50 × 10
-9mol/L, 0.1 × 10
-6mol/L, 0.2 × 10
-6mol/L, 0.5 × 10
-6mol/L, 1 × 10
-6mol/L, 2 × 10
-6mol/L, 5 × 10
-6mol/L, 10 × 10
-6mol/L, 20 × 10
-6mol/L, 50 × 10
-6mol/L, 0.1 × 10
-3mol/L, 0.2 × 10
-3mol/L, 0.5 × 10
-3mol/L, 1 × 10
-3the mercury ion aqueous solution of mol/L, and concussion mixes;
(5), after the carbon point solution left standstill being added with different concns mercury metal ion step (4) obtained 5 minutes, fluorescence intensity detection is carried out;
(6) count the fluorescence intensity of solution in each centrifuge tube in step (5), draw out corresponding matched curve.
The preparation method of Wavelength tunable fluorescent carbon point that the present invention proposes and the application in mercury ion detecting thereof, its advantage is: synthetic method of the present invention is simple, and production efficiency is high, and product quantum yield is high, and cost is low, suitability for scale production.Compared with existing carbon point synthetic method, the inventive method raw material is easy to get, nontoxic, and production process is without the need to special protection and easy control of reaction conditions.The carbon point prepared of the inventive method not only good water solubility, toxicity is extremely low and quantum yield is high, and result is reproducible, can be used for detecting the mercury ion in the aqueous solution, and shows high sensitivity and selectivity, and Concentration Testing limit reaches 1.5 × 10
-9mol/L.
Accompanying drawing explanation
The fluorescent carbon point that Fig. 1 is the embodiment one (in figure 1A, 1B) of the inventive method, prepared by embodiment two (in figure 1C, 1D), embodiment three (in figure 1E, 1F), the photo under 365 nano-ultraviolet lights and indoor white light irradiate.
Fig. 2 is the fluorescence spectrum of blue-fluorescence carbon point when different excitation wavelength prepared by the embodiment one of the inventive method.
Fig. 3 is the fluorescence spectrum of green fluorescence carbon point when different excitation wavelength prepared by the embodiment two of the inventive method.
Fig. 4 is the fluorescence spectrum of yellow fluorescence carbon point when different excitation wavelength prepared by the embodiment three of the inventive method.
Fig. 5 adds the change of fluorescence spectrum and the selectivity cancellation collection of illustrative plates to mercury ion after different metal ion in the green fluorescence carbon point solution tested of the embodiment 13 of the inventive method.
Fig. 6 is the change of fluorescence spectrum after adding different concns mercury ion in the green fluorescence carbon point solution of embodiment 13 test of the inventive method and limits data to the sensitivity technique of mercury ion.
Embodiment
The preparation method of the Wavelength tunable fluorescent carbon point that the present invention proposes, comprises the following steps:
(1) added in 10 ml waters by α-amino-isovaleric acid, the mass percent concentration making α-amino-isovaleric acid is 0.2% ~ 30%, is placed on magnetic stirring apparatus, stirs and α-amino-isovaleric acid is fully dissolved, obtain valine aqueous solution;
(2) by the strong phosphoric acid of 1 ~ 10 milliliter, join in the valine aqueous solution of step (1), continue to be stirred to the solution that solution is homogeneous dispersion;
(3) solution of the homogeneous dispersion of step (2) is put into hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, temperature of reaction is 100 DEG C ~ 120 DEG C, and the reaction times is 2 ~ 24 hours, obtains crude product;
(4) or by the solution of the homogeneous dispersion of step (2) put into water bath with thermostatic control, be placed in stirring reaction on magnetic stirring apparatus, temperature of reaction is 60 DEG C ~ 100 DEG C, and the reaction times is 4 ~ 24 hours, obtains crude product;
(5) by the crude product concentration of step (3) or (4) be in 1 mole of often liter of sodium hydroxide solution and after, by the millipore filtration of 0.22 micron, by precipitation removing, obtain blueness, yellow or the green fluorescence carbon point aqueous solution.
The application of Wavelength tunable fluorescent carbon point in mercury ion detecting prepared by the inventive method, comprises the following steps:
(1) concentration of milligram every milliliter, fluorescent carbon point solution dilution to 1 ~ 5 of being prepared by such as claim 1;
(2) on average join in 9 centrifuge tubes by the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters, respectively to adding 2.5 milliliters in 9 centrifuge tubes, volumetric molar concentration is 5 × 10
-3the sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper, calcium, mercury ion solution, and concussion mixes; Get the fluorescent carbon point solution of dilution and the deionized water of 2.5 milliliters in the step (1) that a centrifuge tube adds 2.5 milliliters in addition, as blank group;
(3) after the fluorescent carbon point solution left standstill being added with metal ion step (2) obtained 5 minutes, spectrophotofluorometer is used to detect the fluorescence intensity of mixing solutions, and contrast with blank group, experimental result shows, the fluorescence intensity cancellation adding the carbon point solution of mercury ion is the most obvious, is added with the carbon point solution fluorescence intensity of other metal ions without considerable change;
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is on average joined in 20 centrifuge tubes, in 20 centrifuge tubes, add 2.5 milliliters respectively, concentration is respectively 0 × 10
-9mol/L, 1 × 10
-9mol/L, 2 × 10
-9mol/L, 5 × 10
-9mol/L, 10 × 10
-9mol/L, 20 × 10
-9mol/L, 50 × 10
-9mol/L, 0.1 × 10
-6mol/L, 0.2 × 10
-6mol/L, 0.5 × 10
-6mol/L, 1 × 10
-6mol/L, 2 × 10
-6mol/L, 5 × 10
-6mol/L, 10 × 10
-6mol/L, 20 × 10
-6mol/L, 50 × 10
-6mol/L, 0.1 × 10
-3mol/L, 0.2 × 10
-3mol/L, 0.5 × 10
-3mol/L, 1 × 10
-3the mercury ion aqueous solution of mol/L, and concussion mixes;
(5), after the carbon point solution left standstill being added with different concns mercury metal ion step (4) obtained 5 minutes, fluorescence intensity detection is carried out;
(6) count the fluorescence intensity of solution in each centrifuge tube in step (5), draw out corresponding matched curve.
Introduce the embodiment of the inventive method below:
Embodiment one:
(1) 1 gram of α-amino-isovaleric acid is added in 10 milliliters of strong phosphoric acid, be placed on magnetic stirring apparatus, fully stir and α-amino-isovaleric acid is fully dissolved, obtain the solution of homogeneous dispersion;
(2) step (1) gained solution is put into hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, temperature of reaction is 120 DEG C, and the reaction times is 4 hours, obtains crude product;
(3) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the blue-fluorescence carbon point aqueous solution.
The photoluminescent property of gained carbon point characterizes: irradiate carbon point aqueous sample with the ultraviolet lamp of wavelength 365 nanometer, can be observed obvious blue fluorescence, as shown in Figure 1B, Figure 1A is the photo of sample under indoor white light.Obtain the carbon point fluorescence spectrum when different excitation wavelength with spectrophotofluorometer, the prepared carbon point of further proved invention sends blue-fluorescence under burst of ultraviolel.Fig. 2 is the obtained fluorescence spectrum of blue-fluorescence carbon point when different excitation wavelength.
Embodiment two:
(1) 1 gram of α-amino-isovaleric acid is added in 10 ml waters, be placed on magnetic stirring apparatus, be stirred to α-amino-isovaleric acid and fully dissolve, obtain 10% valine aqueous solution;
(2) by the strong phosphoric acid of 2 milliliters, join in the solution that step (1) obtains, continue to be stirred to the solution that solution is homogeneous dispersion;
(3) step (2) gained solution is put into water bath with thermostatic control, be placed in stirring reaction on magnetic stirring apparatus, temperature of reaction is 90 DEG C, and the reaction times is 4 hours, obtains crude product;
(4) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the green fluorescence carbon point aqueous solution.
The photoluminescent property of gained carbon point characterizes: irradiate carbon point aqueous sample with the ultraviolet lamp of wavelength 365 nanometer, can be observed obvious green fluorescence, as shown in figure ip, Fig. 1 C is the photo of sample under indoor white light.Obtain the carbon point fluorescence spectrum when different excitation wavelength with spectrophotofluorometer, the prepared carbon point of further proved invention sends green fluorescence under burst of ultraviolel.Fig. 3 is the obtained fluorescence spectrum of green fluorescence carbon point when different excitation wavelength.
Embodiment three:
(1) 1 gram of α-amino-isovaleric acid is added in 10 ml waters, be placed on magnetic stirring apparatus, fully stir and α-amino-isovaleric acid is fully dissolved, obtain 10% valine aqueous solution;
(2) by the strong phosphoric acid of 2 milliliters, join in the solution that 1 milliliter of step (1) obtains, continue to be stirred to the solution that solution is homogeneous dispersion;
(3) step (2) gained solution is put into water bath with thermostatic control, be placed in stirring reaction on magnetic stirring apparatus, temperature of reaction is 90 DEG C, and the reaction times is 10 hours, obtains crude product;
(4) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the yellow fluorescence carbon point aqueous solution.
The photoluminescent property of gained carbon point characterizes: irradiate carbon point aqueous sample with the ultraviolet lamp of wavelength 365 nanometer, can be observed obvious yellow fluorescence, as shown in fig. 1f, Fig. 1 E is the photo of sample under indoor white light.Obtain the carbon point fluorescence spectrum when different excitation wavelength with spectrophotofluorometer, the prepared carbon point of further proved invention sends yellow fluorescence under burst of ultraviolel.Fig. 4 is the obtained fluorescence spectrum of yellow fluorescence carbon point when different excitation wavelength.
Embodiment four:
(1) 0.2 gram of α-amino-isovaleric acid is added in 10 milliliters of strong phosphoric acid, be placed on magnetic stirring apparatus, fully stir and α-amino-isovaleric acid is fully dissolved, obtain the solution of homogeneous dispersion;
(3) step (2) gained solution is put into water bath with thermostatic control, be placed in stirring reaction on magnetic stirring apparatus, temperature of reaction is 60 DEG C, and the reaction times is 4 hours, obtains crude product;
(4) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the blue-fluorescence carbon point aqueous solution.
Embodiment five:
(1) 0.5 gram of α-amino-isovaleric acid is added in 10 ml waters, be placed on magnetic stirring apparatus, be stirred to α-amino-isovaleric acid and fully dissolve, obtain valine aqueous solution;
(2) by the strong phosphoric acid of 9 milliliters, join in the solution that step (1) obtains, continue to be stirred to the solution that solution is homogeneous dispersion;
(3) step (2) gained solution is put into hydrothermal reaction kettle, moves in baking oven and carry out pyrolytic reaction, temperature of reaction is 100 DEG C, and the reaction times is 8 hours, obtains crude product;
(4) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the blue-fluorescence carbon point aqueous solution.
Embodiment six:
(1) 0.4g α-amino-isovaleric acid is added in 10 ml waters, be placed on magnetic stirring apparatus, be stirred to α-amino-isovaleric acid and fully dissolve, obtain valine aqueous solution;
(2) by the strong phosphoric acid of 3 milliliters, join in the solution that step (1) obtains, continue to be stirred to the solution that solution is homogeneous dispersion;
(3) step (2) gained solution is put into hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, temperature of reaction is 100 DEG C, and the reaction times is 8 hours, obtains crude product;
(4) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the green fluorescence carbon point aqueous solution.
Embodiment seven:
(1) 4g α-amino-isovaleric acid is added in 10 ml waters, be placed on magnetic stirring apparatus, be stirred to α-amino-isovaleric acid and fully dissolve, obtain valine aqueous solution;
(2) by the strong phosphoric acid of 4 milliliters, join in the solution that step (1) obtains, continue to be stirred to the solution that solution is homogeneous dispersion;
(3) step (2) gained solution is put into water bath with thermostatic control, be placed in stirring reaction on magnetic stirring apparatus, temperature of reaction is 60 DEG C, and the reaction times is 24 hours, obtains crude product;
(4) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the green fluorescence carbon point aqueous solution.
Embodiment eight:
(1) 4g α-amino-isovaleric acid is added in 10 ml waters, be placed on magnetic stirring apparatus, fully stir and α-amino-isovaleric acid is fully dissolved, obtain valine aqueous solution;
(2) by the strong phosphoric acid of 5 milliliters, join in the solution that step (1) obtains, continue to be stirred to the solution that solution is homogeneous dispersion;
(3) step (2) gained solution is put into water bath with thermostatic control, be placed in stirring reaction on magnetic stirring apparatus, temperature of reaction is 90 DEG C, and the reaction times is 12 hours, obtains crude product;
(4) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the yellow fluorescence carbon point aqueous solution.
Embodiment nine:
(1) 0.3g α-amino-isovaleric acid is added in 10 ml waters, be placed on magnetic stirring apparatus, be stirred to α-amino-isovaleric acid and fully dissolve, obtain valine aqueous solution;
(2) by the strong phosphoric acid of 5 milliliters, join in the solution that step (1) obtains, continue to be stirred to the solution that solution is homogeneous dispersion;
(3) step (2) gained solution is put into water bath with thermostatic control, be placed in stirring reaction on magnetic stirring apparatus, temperature of reaction is 95 DEG C, and the reaction times is 12 hours, obtains crude product;
(4) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the yellow fluorescence carbon point aqueous solution.
Embodiment ten:
(1) 0.2g α-amino-isovaleric acid is added in 10 ml waters, be placed on magnetic stirring apparatus, be stirred to α-amino-isovaleric acid and fully dissolve, obtain valine aqueous solution;
(2) by the strong phosphoric acid of 2 milliliters, join in the solution that step (1) obtains, continue to be stirred to the solution that solution is homogeneous dispersion;
(3) step (2) gained solution is put into hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, temperature of reaction is 120 DEG C, and the reaction times is 10 hours, obtains crude product;
(4) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the yellow fluorescence carbon point aqueous solution.
Embodiment 11:
(1) 3g α-amino-isovaleric acid is added in 10 ml waters, be placed on magnetic stirring apparatus, be stirred to α-amino-isovaleric acid and fully dissolve, obtain valine aqueous solution;
(2) by the strong phosphoric acid of 2 milliliters, join in the solution that step (1) obtains, continue to be stirred to the solution that solution is homogeneous dispersion;
(3) step (2) gained solution is put into hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, temperature of reaction is 120 DEG C, and the reaction times is 10 hours, obtains crude product;
(4) by the crude product of step (3) with in 1 mole of often liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane by precipitation removing, obtain the yellow fluorescence carbon point aqueous solution.
Embodiment 12: the application of blue-fluorescence carbon point in mercury ion detecting.
(1) blue-fluorescence carbon point solution embodiment one, four, five obtained uses deionized water to be diluted to 1mg/ml;
(2) on average join in 9 centrifuge tubes by the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters, respectively to adding 2.5 milliliters in 9 centrifuge tubes, volumetric molar concentration is 5 × 10
-3the sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper, calcium, mercury ion solution, and concussion mixes; Get the fluorescent carbon point solution of dilution and the deionized water of 2.5 milliliters in the step (1) that a centrifuge tube adds 2.5 milliliters in addition, as blank group;
(3) after the fluorescent carbon point solution left standstill being added with metal ion step (2) obtained 5 minutes, spectrophotofluorometer is used to detect the fluorescence intensity of mixing solutions, and contrast with blank group, experimental result shows, the fluorescence intensity cancellation adding the carbon point solution of mercury ion is the most obvious, is added with the carbon point solution fluorescence intensity of other metal ions without considerable change;
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is on average joined in 20 centrifuge tubes, in 20 centrifuge tubes, add 2.5 milliliters respectively, concentration is respectively 0 × 10
-9mol/L, 1 × 10
-9mol/L, 2 × 10
-9mol/L, 5 × 10
-9mol/L, 10 × 10
-9mol/L, 20 × 10
-9mol/L, 50 × 10
-9mol/L, 0.1 × 10
-6mol/L, 0.2 × 10
-6mol/L, 0.5 × 10
-6mol/L, 1 × 10
-6mol/L, 2 × 10
-6mol/L, 5 × 10
-6mol/L, 10 × 10
-6mol/L, 20 × 10
-6mol/L, 50 × 10
-6mol/L, 0.1 × 10
-3mol/L, 0.2 × 10
-3mol/L, 0.5 × 10
-3mol/L, 1 × 10
-3the mercury ion aqueous solution of mol/L, and concussion mixes;
(5), after the carbon point solution left standstill being added with different concns mercury metal ion step (4) obtained 5 minutes, fluorescence intensity detection is carried out;
(6) count the fluorescence intensity of solution in each centrifuge tube in step (5), draw out corresponding matched curve.
Embodiment 13: the application of green fluorescence carbon point in mercury ion detecting.
(1) green fluorescence carbon point solution embodiment two, six, seven obtained uses deionized water to be diluted to 1mg/ml;
(2) on average join in 9 centrifuge tubes by the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters, respectively to adding 2.5 milliliters in 9 centrifuge tubes, volumetric molar concentration is 5 × 10
-3the sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper, calcium, mercury ion solution, and concussion mixes; Get the fluorescent carbon point solution of dilution and the deionized water of 2.5 milliliters in the step (1) that a centrifuge tube adds 2.5 milliliters in addition, as blank group;
(3) after the fluorescent carbon point solution left standstill being added with metal ion step (2) obtained 5 minutes, spectrophotofluorometer is used to detect the fluorescence intensity of mixing solutions, and contrast with blank group, experimental result as shown in Figure 5, the fluorescence intensity cancellation adding the carbon point solution of mercury ion is the most obvious, is added with the carbon point solution fluorescence intensity of other metal ions without considerable change;
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is on average joined in 20 centrifuge tubes, in 20 centrifuge tubes, add 2.5 milliliters respectively, concentration is respectively 0 × 10
-9mol/L, 1 × 10
-9mol/L, 2 × 10
-9mol/L, 5 × 10
-9mol/L, 10 × 10
-9mol/L, 20 × 10
-9mol/L, 50 × 10
-9mol/L, 0.1 × 10
-6mol/L, 0.2 × 10
-6mol/L, 0.5 × 10
-6mol/L, 1 × 10
-6mol/L, 2 × 10
-6mol/L, 5 × 10
-6mol/L, 10 × 10
-6mol/L, 20 × 10
-6mol/L, 50 × 10
-6mol/L, 0.1 × 10
-3mol/L, 0.2 × 10
-3mol/L, 0.5 × 10
-3mol/L, 1 × 10
-3the mercury ion aqueous solution of mol/L, and concussion mixes;
(5), after the carbon point solution left standstill being added with different concns mercury metal ion step (4) obtained 5 minutes, fluorescence intensity detection is carried out;
(6) count the fluorescence intensity of solution in each centrifuge tube in step (5), draw out corresponding matched curve.
The sensitivity technique test-results of green fluorescence carbon point to different concns mercury ion obtained is shown in Fig. 6, and green fluorescence carbon point is to mercury from having higher detection sensitivity, and detectability can reach 1.5nmol/L.
Embodiment 14: the application of yellow fluorescence carbon point in mercury ion detecting.
(1) yellow fluorescence carbon point solution embodiment three, eight, nine, ten, 11 obtained uses deionized water to be diluted to 2 milligrams every milliliter;
(2) on average join in 9 centrifuge tubes by the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters, respectively to adding 2.5 milliliters in 9 centrifuge tubes, volumetric molar concentration is 5 × 10
-3the sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper, calcium, mercury ion solution, and concussion mixes; Get the fluorescent carbon point solution of dilution and the deionized water of 2.5 milliliters in the step (1) that a centrifuge tube adds 2.5 milliliters in addition, as blank group;
(3) after the fluorescent carbon point solution left standstill being added with metal ion step (2) obtained 5 minutes, spectrophotofluorometer is used to detect the fluorescence intensity of mixing solutions, and contrast with blank group, experimental result shows, the fluorescence intensity cancellation adding the carbon point solution of mercury ion is the most obvious, is added with the carbon point solution fluorescence intensity of other metal ions without considerable change;
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is on average joined in 20 centrifuge tubes, in 20 centrifuge tubes, add 2.5 milliliters respectively, concentration is respectively 0 × 10
-9mol/L, 1 × 10
-9mol/L, 2 × 10
-9mol/L, 5 × 10
-9mol/L, 10 × 10
-9mol/L, 20 × 10
-9mol/L, 50 × 10
-9mol/L, 0.1 × 10
-6mol/L, 0.2 × 10
-6mol/L, 0.5 × 10
-6mol/L, 1 × 10
-6mol/L, 2 × 10
-6mol/L, 5 × 10
-6mol/L, 10 × 10
-6mol/L, 20 × 10
-6mol/L, 50 × 10
-6mol/L, 0.1 × 10
-3mol/L, 0.2 × 10
-3mol/L, 0.5 × 10
-3mol/L, 1 × 10
-3the mercury ion aqueous solution of mol/L, and concussion mixes;
(5), after the carbon point solution left standstill being added with different concns mercury metal ion step (4) obtained 5 minutes, fluorescence intensity detection is carried out;
Yellow fluorescence carbon point has detection to mercury metal ion and has higher detection sensitivity, and detectability can reach 4.3nmol/L.
Claims (2)
1. a preparation method for Wavelength tunable fluorescent carbon point, is characterized in that the method comprises the following steps:
(1) added in 10 ml waters by α-amino-isovaleric acid, the mass percent concentration making α-amino-isovaleric acid is 0.2% ~ 30%, is placed on magnetic stirring apparatus, stirs and α-amino-isovaleric acid is fully dissolved, obtain valine aqueous solution;
(2) by the strong phosphoric acid of 1 ~ 10 milliliter, join in the valine aqueous solution of step (1), continue to be stirred to the solution that solution is homogeneous dispersion;
(3) solution of the homogeneous dispersion of step (2) is put into hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, temperature of reaction is 100 DEG C ~ 120 DEG C, and the reaction times is 2 ~ 24 hours, obtains crude product;
(4) or by the solution of the homogeneous dispersion of step (2) put into water bath with thermostatic control, be placed in stirring reaction on magnetic stirring apparatus, temperature of reaction is 60 DEG C ~ 100 DEG C, and the reaction times is 4 ~ 24 hours, obtains crude product;
(5) by the crude product concentration of step (3) or (4) be in 1 mole of often liter of sodium hydroxide solution and after, by the millipore filtration of 0.22 micron, by precipitation removing, obtain blueness, yellow or the green fluorescence carbon point aqueous solution.
2. the application of Wavelength tunable fluorescent carbon point in mercury ion detecting prepared of claim 1, comprises the following steps: the concentration of milligram every milliliter, (1) fluorescent carbon point solution dilution to 1 ~ 5 of such as claim 1 being prepared;
(2) on average join in 9 centrifuge tubes by the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters, respectively to adding 2.5 milliliters in 9 centrifuge tubes, volumetric molar concentration is 5 × 10
-3the sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper, calcium, mercury ion solution, and concussion mixes; Get the fluorescent carbon point solution of dilution and the deionized water of 2.5 milliliters in the step (1) that a centrifuge tube adds 2.5 milliliters in addition, as blank group;
(3) after the fluorescent carbon point solution left standstill being added with metal ion step (2) obtained 5 minutes, spectrophotofluorometer is used to detect the fluorescence intensity of mixing solutions, and contrast with blank group, experimental result shows, the fluorescence intensity cancellation adding the carbon point solution of mercury ion is the most obvious, is added with the carbon point solution fluorescence intensity of other metal ions without considerable change;
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is on average joined in 20 centrifuge tubes, in 20 centrifuge tubes, add 2.5 milliliters respectively, concentration is respectively 0 × 10
-9mol/L, 1 × 10
-9mol/L, 2 × 10
-9mol/L, 5 × 10
-9mol/L, 10 × 10
-9mol/L, 20 × 10
-9mol/L, 50 × 10
-9mol/L, 0.1 × 10
-6mol/L, 0.2 × 10
-6mol/L, 0.5 × 10
-6mol/L, 1 × 10
-6mol/L, 2 × 10
-6mol/L, 5 × 10
-6mol/L, 10 × 10
-6mol/L, 20 × 10
-6mol/L, 50 × 10
-6mol/L, 0.1 × 10
-3mol/L, 0.2 × 10
-3mol/L, 0.5 × 10
-3mol/L, 1 × 10
-3the mercury ion aqueous solution of mol/L, and concussion mixes;
(5), after the carbon point solution left standstill being added with different concns mercury metal ion step (4) obtained 5 minutes, fluorescence intensity detection is carried out;
(6) count the fluorescence intensity of solution in each centrifuge tube in step (5), draw out corresponding matched curve.
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