CN104610964B - The preparation method of Wavelength tunable fluorescent carbon point and the application in mercury ion detecting thereof - Google Patents
The preparation method of Wavelength tunable fluorescent carbon point and the application in mercury ion detecting thereof Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of Wavelength tunable fluorescent carbon point and the application in mercury ion detecting thereof, belong to technical field of nano material.This method, with valine as raw material, obtains having long wavelength, the photochromic adjustable carbon point aqueous solution of fluorescence by hydrothermal synthesis method.The inventive method only needs phosphoric acid to regulate, and raw material is easy to get, nontoxic, and production process has the advantages such as productivity is high, quantum efficiency is high, result is reproducible without special protection, easy control of reaction conditions, obtained carbon point.The inventive method has that productivity is high, preparation technology simple, low cost, be prone to the features such as large-scale production.The carbon point prepared by this method may be used for the high selectivity of mercury ion, high-sensitivity detection, and detection limit reaches 1.5 × 10‑9Mol/L.
Description
Technical field
The present invention relates to the preparation method of a kind of Wavelength tunable fluorescent carbon point and the application in mercury ion detecting thereof, belong to nanometer
Field of material technology.
Background technology
Mercury ion is one of heavy metal ion that toxicity is the strongest, is considered the dirt the most universal and the most dangerous to human health and environment
One of dye thing.It is revealed, contact high concentration mercury ion can to the human health serious toxic action of induction, as brain damage, in
Pivot nervous system infringement, internal system infringement and various cognition and dyskinesia etc..Accordingly, it would be desirable to mercury ion is had by exploitation
There are high selectivity and sensitivity, and simple and efficient detection method.So far, the method for mercury ion detecting is mainly wrapped
Include Atomic Absorption Spectrometer, atomic fluorescence spectrometry, inductivity coupled plasma mass spectrometry, selective cold-atomic fluorescence spectrometry
With electrochemical process etc..But, these methods need complicated Sample Preparation Procedure and accurate instrument, which greatly limits
They actual application in conventional mercury ion detecting.Therefore, mercury ion high sensitivity, high selective simplicity in exploitation water
Detection method remains a huge challenge efficiently.In order to solve these problems, various chemical sensors, as fluorescence passes
Sensors etc. have been developed that, and for mercury ion detecting.Fluorescent carbon point is a kind of New Type of Carbon nano particle occurred recent years,
Because the features such as good water solubility, toxicity are extremely low and photoluminescent property is stable have important in terms of bio-imaging and metal ion detection
Application prospect.The synthetic method of carbon point mainly includes prepared by nitric acid oxidation method, Electrochemical preparation method, pyrolysismethod, laser ablation
Method, template, Microwave-assisted synthesis method etc..But, the carbon most of excitation wavelength of point synthesized by these methods is the shortest
Blue-fluorescence, and longer wavelengths of green or yellow fluorescence carbon point report are seldom, and quantum yield is the lowest.
Summary of the invention
The purpose of the present invention is to propose to the preparation method of a kind of Wavelength tunable fluorescent carbon point and the application in mercury ion detecting thereof,
With simplify Wavelength tunable fluorescent carbon point preparation technology, reduce preparation cost, and make the carbon point of preparation can be used for detect mercury from
Son, improves sensitivity and the selectivity of mercury ion detecting, and 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) being added to by valine in 10 milliliters of water, the mass percent concentration making valine is 0.2%～30%, is placed in
On magnetic stirring apparatus, stirring makes valine fully dissolve, and obtains valine aqueous solution；
(2) by the SPA of 1～10 milliliter, join in the valine aqueous solution of step (1), continue stirring to solution
For homogeneous scattered solution；
(3) the homogeneous scattered solution of step (2) is put in hydrothermal reaction kettle, moves in baking oven and carry out pyrolytic reaction,
Reaction temperature is 100 DEG C～120 DEG C, and the reaction time is 2～24 hours, obtains crude product；
(4) or the homogeneous scattered solution of step (2) is put in water bath with thermostatic control, is placed on magnetic stirring apparatus stirring reaction,
Reaction temperature is 60 DEG C～100 DEG C, and the reaction time is 4～24 hours, obtains crude product；
(5) by the crude product concentration of step (3) or (4) be in 1 mole of every liter of sodium hydroxide solution and after, logical
Cross the miillpore filter of 0.22 micron, precipitation is removed, obtains blueness, yellow or the green fluorescent carbon dots aqueous solution.
Wavelength tunable fluorescent carbon point prepared by the inventive method application in mercury ion detecting, comprises the following steps:
(1) fluorescent carbon point solution prepared by such as claim 1 is diluted to the concentration of 1～5 milligram every milliliter；
(2) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 9 centrifuge tubes, respectively
In 9 centrifuge tubes, addition 2.5 milliliters, molar concentration are 5 × 10-3The sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper,
Calcium, mercury ion solution, and shake mix；Additionally take the middle dilution of step (1) that a centrifuge tube adds 2.5 milliliters
Fluorescent carbon point solution and the deionized water of 2.5 milliliters, as blank group；
(3), after the fluorescent carbon point solution left standstill 5 minutes added with metal ion step (2) obtained, fluorescence is used to divide
The fluorescence intensity of light photometer detection mixed solution, and contrast with blank group, experimental result shows, adds mercury ion
The fluorescence intensity cancellation of carbon point solution is the most obvious, added with the carbon point solution fluorescence intensity of other metal ions without significant change；
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 20 centrifuge tubes, to
20 centrifuge tubes are separately added into 2.5 milliliters, concentration be 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 shake mix；
(5), after the carbon point solution left standstill 5 minutes added with variable concentrations mercury metal ion step (4) obtained, carry out
Fluorescence intensity detects；
(6) count in step (5) fluorescence intensity of solution in each centrifuge tube, draw out corresponding matched curve.
The preparation method of the 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 low cost is suitable for scale production.With existing
Carbon point synthetic method compare, the inventive method raw material is easy to get, nontoxic, and production process is held without special protection and reaction condition
Easy to control.Carbon point not only good water solubility prepared by the inventive method, 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 show high sensitivity and selectivity, Concentration Testing limit reaches 1.5 ×
10-9Mol/L.
Accompanying drawing explanation
Fig. 1 is the embodiment one (1A, 1B in figure) of the inventive method, embodiment two (1C, 1D in figure), embodiment
Fluorescent carbon point prepared by three (1E, 1F in figure), the photo under 365 nano-ultraviolet lights and indoor white light irradiate.
Fig. 2 is the blue-fluorescence carbon point of embodiment one preparation of the inventive method fluorescence spectrum when different excitation wavelength.
Fig. 3 is the green fluorescent carbon dots of embodiment two preparation of the inventive method fluorescence spectrum when different excitation wavelength.
Fig. 4 is the yellow fluorescence carbon point of embodiment three preparation of the inventive method fluorescence spectrum when different excitation wavelength.
Fig. 5 be embodiment 13 test of the inventive method green fluorescent carbon dots solution in add fluorescence after different metal ion
The change of spectrum and the selective cancellation collection of illustrative plates to mercury ion.
Fig. 6 be embodiment 13 test of the inventive method green fluorescent carbon dots solution in add after variable concentrations mercury ion glimmering
The change of light spectrum and the sensitivity technique limit data to mercury ion.
Detailed description of the invention
The preparation method of the Wavelength tunable fluorescent carbon point that the present invention proposes, comprises the following steps:
(1) being added to by valine in 10 milliliters of water, the mass percent concentration making valine is 0.2%～30%, is placed in
On magnetic stirring apparatus, stirring makes valine fully dissolve, and obtains valine aqueous solution；
(2) by the SPA of 1～10 milliliter, join in the valine aqueous solution of step (1), continue stirring to solution
For homogeneous scattered solution；
(3) the homogeneous scattered solution of step (2) is put in hydrothermal reaction kettle, moves in baking oven and carry out pyrolytic reaction,
Reaction temperature is 100 DEG C～120 DEG C, and the reaction time is 2～24 hours, obtains crude product；
(4) or the homogeneous scattered solution of step (2) is put in water bath with thermostatic control, is placed on magnetic stirring apparatus stirring reaction,
Reaction temperature is 60 DEG C～100 DEG C, and the reaction time is 4～24 hours, obtains crude product；
(5) by the crude product concentration of step (3) or (4) be in 1 mole of every liter of sodium hydroxide solution and after, logical
Cross the miillpore filter of 0.22 micron, precipitation is removed, obtains blueness, yellow or the green fluorescent carbon dots aqueous solution.
Wavelength tunable fluorescent carbon point prepared by the inventive method application in mercury ion detecting, comprises the following steps:
(1) fluorescent carbon point solution prepared by such as claim 1 is diluted to the concentration of 1～5 milligram every milliliter；
(2) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 9 centrifuge tubes, respectively
In 9 centrifuge tubes, addition 2.5 milliliters, molar concentration are 5 × 10-3The sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper,
Calcium, mercury ion solution, and shake mix；Additionally take the middle dilution of step (1) that a centrifuge tube adds 2.5 milliliters
Fluorescent carbon point solution and the deionized water of 2.5 milliliters, as blank group；
(3), after the fluorescent carbon point solution left standstill 5 minutes added with metal ion step (2) obtained, fluorescence is used to divide
The fluorescence intensity of light photometer detection mixed solution, and contrast with blank group, experimental result shows, adds mercury ion
The fluorescence intensity cancellation of carbon point solution is the most obvious, added with the carbon point solution fluorescence intensity of other metal ions without significant change；
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 20 centrifuge tubes, to
20 centrifuge tubes are separately added into 2.5 milliliters, concentration be 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 shake mix；
(5), after the carbon point solution left standstill 5 minutes added with variable concentrations mercury metal ion step (4) obtained, carry out
Fluorescence intensity detects；
(6) count in step (5) fluorescence intensity of solution in each centrifuge tube, draw out corresponding matched curve.
The embodiment of the inventive method be described below:
Embodiment one:
(1) 1 gram of valine is added in 10 milliliters of SPAs, be placed on magnetic stirring apparatus, be sufficiently stirred for making valine
Fully dissolve, obtain homogeneous scattered solution；
(2) step (1) gained solution is put in hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, reaction temperature
Being 120 DEG C, the reaction time is 4 hours, obtains crude product；
(3) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter membrane
Precipitation is removed, obtains the blue-fluorescence carbon point aqueous solution.
The photoluminescent property of gained carbon point characterizes: be irradiated carbon point aqueous sample with the uviol lamp of wavelength 365 nanometer,
Obvious blue fluorescence be can be observed, and as shown in Figure 1B, Figure 1A is the photo of sample under indoor white light.Use fluorescence spectrophotometer light
Degree meter obtains the carbon point fluorescence spectrum when different excitation wavelength, is further characterized by carbon point prepared by the present invention under burst of ultraviolel
Send blue-fluorescence.Fig. 2 is the obtained blue-fluorescence carbon point fluorescence spectrum when different excitation wavelength.
Embodiment two:
(1) being added in 10 milliliters of water by 1 gram of valine, be placed on magnetic stirring apparatus, stirring to valine is fully dissolved,
Obtain 10% valine aqueous solution；
(2) by the SPA of 2 milliliters, joining in the solution obtained by step (1), continuing stirring is homogeneous to solution
Scattered solution；
(3) step (2) gained solution is put in water bath with thermostatic control, be placed on magnetic stirring apparatus stirring reaction, reaction temperature
Being 90 DEG C, the reaction time is 4 hours, obtains crude product；
(4) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter
Precipitation is removed by film, obtains the green fluorescent carbon dots aqueous solution.
The photoluminescent property of gained carbon point characterizes: be irradiated carbon point aqueous sample with the uviol lamp of wavelength 365 nanometer,
Obvious green fluorescence be can be observed, and as shown in figure ip, Fig. 1 C is the photo of sample under indoor white light.Use fluorescence spectrophotometer light
Degree meter obtains the carbon point fluorescence spectrum when different excitation wavelength, is further characterized by carbon point prepared by the present invention under burst of ultraviolel
Send green fluorescence.Fig. 3 is the obtained green fluorescent carbon dots fluorescence spectrum when different excitation wavelength.
Embodiment three:
(1) 1 gram of valine is added in 10 milliliters of water, be placed on magnetic stirring apparatus, be sufficiently stirred for making valine abundant
Dissolve, obtain 10% valine aqueous solution；
(2) by the SPA of 2 milliliters, join in the solution obtained by 1 milliliter of step (1), continue stirring to solution
For homogeneous scattered solution；
(3) step (2) gained solution is put in water bath with thermostatic control, be placed on magnetic stirring apparatus stirring reaction, reaction temperature
Being 90 DEG C, the reaction time is 10 hours, obtains crude product；
(4) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter
Precipitation is removed by film, obtains the yellow fluorescence carbon point aqueous solution.
The photoluminescent property of gained carbon point characterizes: be irradiated carbon point aqueous sample with the uviol lamp of wavelength 365 nanometer,
Obvious yellow fluorescence be can be observed, and as shown in fig. 1f, Fig. 1 E is the photo of sample under indoor white light.Use fluorescence spectrophotometer light
Degree meter obtains the carbon point fluorescence spectrum when different excitation wavelength, is further characterized by carbon point prepared by the present invention under burst of ultraviolel
Send yellow fluorescence.Fig. 4 is the obtained yellow fluorescence carbon point fluorescence spectrum when different excitation wavelength.
Embodiment four:
(1) 0.2 gram of valine is added in 10 milliliters of SPAs, be placed on magnetic stirring apparatus, be sufficiently stirred for making figured silk fabrics ammonia
Acid is fully dissolved, and obtains homogeneous scattered solution；
(3) step (2) gained solution is put in water bath with thermostatic control, be placed on magnetic stirring apparatus stirring reaction, reaction temperature
Being 60 DEG C, the reaction time is 4 hours, obtains crude product；
(4) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter
Precipitation is removed by film, obtains the blue-fluorescence carbon point aqueous solution.
Embodiment five:
(1) 0.5 gram of valine is added in 10 milliliters of water, be placed on magnetic stirring apparatus, stir the most molten to valine
Solve, obtain valine aqueous solution；
(2) by the SPA of 9 milliliters, joining in the solution obtained by step (1), continuing stirring is homogeneous to solution
Scattered solution；
(3) step (2) gained solution is put in hydrothermal reaction kettle, moves in baking oven and carry out pyrolytic reaction, reaction temperature
Degree is 100 DEG C, and the reaction time is 8 hours, obtains crude product；
(4) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter
Precipitation is removed by film, obtains the blue-fluorescence carbon point aqueous solution.
Embodiment six:
(1) 0.4g valine is added in 10 milliliters of water, be placed on magnetic stirring apparatus, stir the most molten to valine
Solve, obtain valine aqueous solution；
(2) by the SPA of 3 milliliters, joining in the solution obtained by step (1), continuing stirring is homogeneous to solution
Scattered solution；
(3) step (2) gained solution is put in hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, reaction temperature
Being 100 DEG C, the reaction time is 8 hours, obtains crude product；
(4) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter
Precipitation is removed by film, obtains the green fluorescent carbon dots aqueous solution.
Embodiment seven:
(1) being added in 10 milliliters of water by 4g valine, be placed on magnetic stirring apparatus, stirring to valine is fully dissolved,
Obtain valine aqueous solution；
(2) by the SPA of 4 milliliters, joining in the solution obtained by step (1), continuing stirring is homogeneous to solution
Scattered solution；
(3) step (2) gained solution is put in water bath with thermostatic control, be placed on magnetic stirring apparatus stirring reaction, reaction temperature
Being 60 DEG C, the reaction time is 24 hours, obtains crude product；
(4) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter
Precipitation is removed by film, obtains the green fluorescent carbon dots aqueous solution.
Embodiment eight:
(1) 4g valine is added in 10 milliliters of water, be placed on magnetic stirring apparatus, be sufficiently stirred for making valine abundant
Dissolve, obtain valine aqueous solution；
(2) by the SPA of 5 milliliters, joining in the solution obtained by step (1), continuing stirring is homogeneous to solution
Scattered solution；
(3) step (2) gained solution is put in water bath with thermostatic control, be placed on magnetic stirring apparatus stirring reaction, reaction temperature
Being 90 DEG C, the reaction time is 12 hours, obtains crude product；
(4) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter
Precipitation is removed by film, obtains the yellow fluorescence carbon point aqueous solution.
Embodiment nine:
(1) 0.3g valine is added in 10 milliliters of water, be placed on magnetic stirring apparatus, stir the most molten to valine
Solve, obtain valine aqueous solution；
(2) by the SPA of 5 milliliters, joining in the solution obtained by step (1), continuing stirring is homogeneous to solution
Scattered solution；
(3) step (2) gained solution is put in water bath with thermostatic control, be placed on magnetic stirring apparatus stirring reaction, reaction temperature
Being 95 DEG C, the reaction time is 12 hours, obtains crude product；
(4) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter
Precipitation is removed by film, obtains the yellow fluorescence carbon point aqueous solution.
Embodiment ten:
(1) 0.2g valine is added in 10 milliliters of water, be placed on magnetic stirring apparatus, stir the most molten to valine
Solve, obtain valine aqueous solution；
(2) by the SPA of 2 milliliters, joining in the solution obtained by step (1), continuing stirring is homogeneous to solution
Scattered solution；
(3) step (2) gained solution is put in hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, reaction temperature
Being 120 DEG C, the reaction time is 10 hours, obtains crude product；
(4) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter
Precipitation is removed by film, obtains the yellow fluorescence carbon point aqueous solution.
Embodiment 11:
(1) being added in 10 milliliters of water by 3g valine, be placed on magnetic stirring apparatus, stirring to valine is fully dissolved,
Obtain valine aqueous solution；
(2) by the SPA of 2 milliliters, joining in the solution obtained by step (1), continuing stirring is homogeneous to solution
Scattered solution；
(3) step (2) gained solution is put in hydrothermal reaction kettle, move in baking oven and carry out pyrolytic reaction, reaction temperature
Being 120 DEG C, the reaction time is 10 hours, obtains crude product；
(4) by the crude product of step (3) with in 1 mole of every liter of sodium hydroxide solution and after, by 0.22 micrometer Millipore filter
Precipitation is removed by film, obtains the yellow fluorescence carbon point aqueous solution.
Embodiment 12: blue-fluorescence carbon point application in mercury ion detecting.
(1) deionized water is used to be diluted to 1mg/ml the blue-fluorescence carbon point solution obtained by embodiment one, four, five；
(2) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 9 centrifuge tubes, respectively
In 9 centrifuge tubes, addition 2.5 milliliters, molar concentration are 5 × 10-3The sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper,
Calcium, mercury ion solution, and shake mix；Additionally take the middle dilution of step (1) that a centrifuge tube adds 2.5 milliliters
Fluorescent carbon point solution and the deionized water of 2.5 milliliters, as blank group；
(3), after the fluorescent carbon point solution left standstill 5 minutes added with metal ion step (2) obtained, fluorescence is used to divide
The fluorescence intensity of light photometer detection mixed solution, and contrast with blank group, experimental result shows, adds mercury ion
The fluorescence intensity cancellation of carbon point solution is the most obvious, added with the carbon point solution fluorescence intensity of other metal ions without significant change；
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 20 centrifuge tubes, to
20 centrifuge tubes are separately added into 2.5 milliliters, concentration be 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 shake mix；
(5), after the carbon point solution left standstill 5 minutes added with variable concentrations mercury metal ion step (4) obtained, carry out
Fluorescence intensity detects；
(6) count in step (5) fluorescence intensity of solution in each centrifuge tube, draw out corresponding matched curve.
Embodiment 13: green fluorescent carbon dots application in mercury ion detecting.
(1) deionized water is used to be diluted to 1mg/ml the green fluorescent carbon dots solution obtained by embodiment two, six, seven；
(2) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 9 centrifuge tubes, respectively
In 9 centrifuge tubes, addition 2.5 milliliters, molar concentration are 5 × 10-3The sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper,
Calcium, mercury ion solution, and shake mix；Additionally take the middle dilution of step (1) that a centrifuge tube adds 2.5 milliliters
Fluorescent carbon point solution and the deionized water of 2.5 milliliters, as blank group；
(3), after the fluorescent carbon point solution left standstill 5 minutes added with metal ion step (2) obtained, fluorescence is used to divide
The fluorescence intensity of light photometer detection mixed solution, and contrast with blank group, experimental result is as it is shown in figure 5, add mercury
The fluorescence intensity cancellation of the carbon point solution of ion is the most obvious, added with the carbon point solution fluorescence intensity of other metal ions without substantially
Change；
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 20 centrifuge tubes, to
20 centrifuge tubes are separately added into 2.5 milliliters, concentration be 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 shake mix；
(5), after the carbon point solution left standstill 5 minutes added with variable concentrations mercury metal ion step (4) obtained, carry out
Fluorescence intensity detects；
(6) count in step (5) fluorescence intensity of solution in each centrifuge tube, draw out corresponding matched curve.
The sensitivity technique result of the test of variable concentrations mercury ion is shown in Fig. 6, green fluorescence carbon by obtained green fluorescent carbon dots
Point is to mercury from having higher detection sensitivity, and detection limit is up to 1.5nmol/L.
Embodiment 14: yellow fluorescence carbon point application in mercury ion detecting.
(1) the yellow fluorescence carbon point solution obtained by embodiment three, eight, nine, ten, 11 is used deionized water dilution
To 2 milligrams every milliliter；
(2) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 9 centrifuge tubes, respectively
In 9 centrifuge tubes, addition 2.5 milliliters, molar concentration are 5 × 10-3The sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper,
Calcium, mercury ion solution, and shake mix；Additionally take the middle dilution of step (1) that a centrifuge tube adds 2.5 milliliters
Fluorescent carbon point solution and the deionized water of 2.5 milliliters, as blank group；
(3), after the fluorescent carbon point solution left standstill 5 minutes added with metal ion step (2) obtained, fluorescence is used to divide
The fluorescence intensity of light photometer detection mixed solution, and contrast with blank group, experimental result shows, adds mercury ion
The fluorescence intensity cancellation of carbon point solution is the most obvious, added with the carbon point solution fluorescence intensity of other metal ions without significant change；
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 20 centrifuge tubes, to
20 centrifuge tubes are separately added into 2.5 milliliters, concentration be 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 shake mix；
(5), after the carbon point solution left standstill 5 minutes added with variable concentrations mercury metal ion step (4) obtained, carry out
Fluorescence intensity detects；
Yellow fluorescence carbon point has detection and has a higher detection sensitivity mercury metal ion, detection limit up to
4.3nmol/L。
Claims (1)
1. a Wavelength tunable fluorescent carbon point application in mercury ion detecting, comprises the following steps: it is characterized in that, including
The preparation of Wavelength tunable fluorescent carbon point and the application two parts in mercury ion detecting；The preparation of described Wavelength tunable fluorescent carbon point
Comprise the following steps: valine is added in 10 milliliters of water by (1), make the mass percent concentration of valine be 0.2%～
30%, it is placed on magnetic stirring apparatus, stirring makes valine fully dissolve, and obtains valine aqueous solution；
(2) by the SPA of 1～10 milliliter, join in the valine aqueous solution of step (1), continue stirring to solution
For homogeneous scattered solution；
(3) the homogeneous scattered solution of step (2) is put in hydrothermal reaction kettle, moves in baking oven and carry out pyrolytic reaction,
Reaction temperature is 100 DEG C～120 DEG C, and the reaction time is 2～24 hours, obtains crude product；
(4) or the homogeneous scattered solution of step (2) is put in water bath with thermostatic control, is placed on magnetic stirring apparatus stirring reaction,
Reaction temperature is 60 DEG C～100 DEG C, and the reaction time is 4～24 hours, obtains crude product；
(5) by the crude product concentration of step (3) or (4) be in 1 mole of every liter of sodium hydroxide solution and after, logical
Cross the miillpore filter of 0.22 micron, precipitation is removed, obtains blueness, yellow or the green fluorescent carbon dots aqueous solution；
The application in mercury ion detecting of the described adjustable fluorescent carbon point, comprises the following steps:
(1) fluorescent carbon point solution prepared by such as claim 1 is diluted to the concentration of 1～5 milligram every milliliter；
(2) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 9 centrifuge tubes, respectively
In 9 centrifuge tubes, addition 2.5 milliliters, molar concentration are 5 × 10-3The sodium of mol/L, potassium, nickel, manganese, iron, magnesium, copper,
Calcium, mercury ion solution, and shake mix；Additionally take the middle dilution of step (1) that a centrifuge tube adds 2.5 milliliters
Fluorescent carbon point solution and the deionized water of 2.5 milliliters, as blank group；
(3), after the fluorescent carbon point solution left standstill 5 minutes added with metal ion step (2) obtained, fluorescence is used to divide
The fluorescence intensity of light photometer detection mixed solution, and contrast with blank group, experimental result shows, adds mercury ion
The fluorescence intensity cancellation of carbon point solution is the most obvious, added with the carbon point solution fluorescence intensity of other metal ions without significant change；
(4) the fluorescent carbon point solution of dilution in the step (1) of 2.5 milliliters is averagely joined in 20 centrifuge tubes, to
20 centrifuge tubes are separately added into 2.5 milliliters, concentration be 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 shake mix；
(5), after the carbon point solution left standstill 5 minutes added with variable concentrations mercury metal ion step (4) obtained, carry out
Fluorescence intensity detects；
(6) count in step (5) fluorescence intensity of solution in each centrifuge tube, draw out corresponding matched curve.
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