CN110044857A - A kind of preparation method of fluorescent carbon point and its application in Visual retrieval ferric ion - Google Patents
A kind of preparation method of fluorescent carbon point and its application in Visual retrieval ferric ion Download PDFInfo
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- CN110044857A CN110044857A CN201910295814.5A CN201910295814A CN110044857A CN 110044857 A CN110044857 A CN 110044857A CN 201910295814 A CN201910295814 A CN 201910295814A CN 110044857 A CN110044857 A CN 110044857A
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- G—PHYSICS
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- 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
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
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- 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
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
A kind of preparation method of fluorescent carbon point, it is characterised in that include the following steps: that methacrylic acid and m-phenylene diamine (MPD) that molar ratio is 1~3:1 are dissolved in the deionized water of 15~30 times of equivalents, obtain solution A using the methacrylic acid of an equivalent as calculating benchmark；Solution A is transferred in hydrothermal reaction kettle, 60~200 DEG C are heated to after closed and is reacted, the reaction time 0.5~5 hour, cooled to room temperature, obtained solution B after reaction；Solution B is centrifuged, is dried, is re-dissolved as carbon dots fluorescence test solution.The invention also discloses above-mentioned fluorescent carbon point test solution Visual retrieval ferric ion application.Compared with prior art, preparation method of the invention is simple, quick, safe, and raw material is easy to get, is cheap；Carbon dots fluorescence test solution or test paper obtained are high to the selectivity of metal ion, and phenomenon is obvious, can easily realize Fe3+Qualitative, sxemiquantitative and quantitative detection.
Description
Technical field
The invention belongs to detection of heavy metal ion reagent technique fields, and in particular to a kind of preparation method of fluorescent carbon point and
Application of the fluorescent carbon point in Visual retrieval ferric ion.
Background technique
With the development of industry and the growing improvement of living standard of the people, using heavy metal ion as the dirt of representative
Dye object is largely discharged into environment, such as soil, water, vegetation.These metal ions can remain in environment for a long time, thus produce
The pollution of duration is given birth to.Wherein iron ion is a metal ion species distributed more widely in environment.Iron in human body with blood red egg
White combination plays an important role in human body for conveying oxygen；Secondly, the shortage of iron will cause many changes physiologically
Change, such as body immunity can be made low, leads to anaemia etc.；However it can draw after entering human body to remaining Fe supply in environment
Play human-body biological system disorders.Therefore, the detection of iron ion has great importance in fields such as biomedicine, environment.
Conventional metals ion detection technology, such as: atomic absorption spectrography (AAS) (AAS), atomic emission spectrometry (AES), electricity
Sense coupling plasma transmitting mass spectrography (ICP-MS), anodic stripping voltammetry (ASV) etc. can detect iron ion, and these are examined
Survey technology selectivity with higher and accuracy.But expensive equipment needed for these detection techniques, at high cost, time-consuming, pre-
It handles cumbersome and professional is needed to operate.Thus a kind of new metal ion detection technology-Visual retrieval comes into being.It can
It is a kind of Fast Detection Technique emerging in recent years depending on changing detection (Visual Detection, VD) technology, is known using sensor
Do not achieve the purpose that/semi-quantitative analysis qualitative to object.By to the optical signal generated in object identification process for example
Color, fluorescence etc. quickly judge analysis result.These Visual retrieval sensors be typically all observe by the naked eye or
Person observes the variation on fluorescence visual to judge the presence of object.
Carbon nanomaterial is a kind of novel fluorescence nanoparticle occurred in recent years.This nano material not only has excellent
Optical property and small size property, and have good biocompatibility and hypotoxicity, allow them to be applied to
Multiple fields.Such as application No. is the application for a patent for invention of CN201611214901.6 " the preparation sides of the carbon nano dot based on mangosteen
Method and its application as fluorescence probe detection ferric ion " carbon nanometer disclosed in (application publication number CN106629663A)
Point the preparation method comprises the following steps: by mangosteen pulp be put into crucible roasting drying, obtain solid；The solid is heated on electrothermal furnace again,
Until after the color of solid becomes yellowish-brown by white, it is cooling, it crushes, obtains yellowish-brown powder；By yellowish-brown powder with ultrapure
Supernatant is extracted in water dissolution, magnetic agitation, ultrasound, centrifugation；By supernatant liquid filtering, dialysis is true by obtained carbon nanodot solution
Sky is dry, crushes to get carbon nano dot powder (MCDs) is arrived.It is mutual with iron ion that the carbon nano dot powder can be used as fluorescence probe
Effect, makes MCDs fluorescent quenching and forms MCDs-Fe3+Compound, to realize the detection to ferric ion.But this application
The middle raw material for preparing carbon nano dot powder i.e. mangosteen limited amount, and raw material has region limitation, is not easy to implement.
For another example application No. is the patent of invention of CN201510013814.3 " a kind of ferric ion fluorescent probe compounds and
Its preparation and application " (Authorization Notice No. CN104496997B) disclose a kind of ferric ion fluorescent probe compounds and its
Preparation and application.The preparation method of the iron-ion fluorescent probe compound is: rhodamine B mixed with anhydrous ethylenediamine, and
It flows back in ethanol and the amide of rhodamine is made；The hydroxyl that dinaphthol is protected with chloromethyl methyl ether, under the action of butyl lithium, with
After n,N-Dimethylformamide reaction, methyl ether methyl is sloughed with hydrochloric acid, obtains the dinaphthol with aldehyde radical；Finally by the acyl of rhodamine
Amine flows back in ethanol with the dinaphthol with aldehyde radical, washs, obtains the fluorescent probe compounds of pure ferric ion.It should
Probe compound has good selectivity to ferric ion and sensitivity, and test sample pre-treatment is simple, and to cell
There is no toxicity, the detection for the ferric ion in water body environment and biological cell.But the preparation method of the patent compared with
Complexity is equally not easy to implement.
Design as a result, it is a kind of it is cheap, easy be easy to get, green safe fluorescent carbon point material is in detection of heavy metal ion
Field is of great significance.
Summary of the invention
First technical problem to be solved by this invention is the status for the prior art, provide it is a kind of cost is relatively low,
Simplicity is easy to get and the preparation method of green safe fluorescent carbon point.
Second technical problem to be solved by this invention is the status for the prior art, provides a kind of above method system
Application of the fluorescent carbon point obtained in Visual retrieval ferric ion.
The present invention solves technical solution used by above-mentioned first technical problem are as follows: a kind of preparation side of fluorescent carbon point
Method, it is characterised in that include the following steps: using the methacrylic acid of an equivalent as calculating benchmark, be 1~3:1's by molar ratio
Methacrylic acid and m-phenylene diamine (MPD) are dissolved in the deionized water of 15~30 times of equivalents, obtain solution A；Then solution A is transferred to
In hydrothermal reaction kettle, it is heated to 60~200 DEG C after closed and is reacted, it is the reaction time 0.5~5 hour, natural after reaction
It is cooled to room temperature, obtains solution B；Above-mentioned solution B is centrifuged, 10000~15000rpm of centrifugal rotational speed, centrifugation time 5~
10min, gained supernatant liquor obtains carbon dots fluorescent powder by freeze-drying after centrifugation, and it is glimmering to re-dissolve carbon dots with deionized water
Light powder is prepared into the carbon dots fluorescence test solution of 0.1~0.5g/L.
The present invention solves technical solution used by above-mentioned second technical problem are as follows: a kind of preparation method as described above
Application of the carbon dots fluorescence test solution obtained in Visual retrieval ferric ion.
Impregnated 0.5~3 hour as an improvement, filter paper is put into above-mentioned carbon dots fluorescence test solution, further take out naturally dry or
Cold wind drying obtains fluorescent test paper.Fluorescent test paper and carbon dots fluorescence test solution can directly detect ferric ion, without borrowing
Help other equipment.
It is further improved, the method for the carbon dots fluorescence test solution or fluorescent test paper detection ferric ion includes qualitative inspection
Survey, half-quantitative detection and quantitative detection.
The method of the carbon dots fluorescence test solution or fluorescent test paper qualitative detection ferric ion is preferred are as follows: drips solution to be measured
It is added in carbon dots fluorescence test solution or (solution to be measured dropwise addition 5 is preferably dripped into 1mL carbon dots fluorescence with rubber head dropper on fluorescent test paper
In test solution or on fluorescent test paper), the color of carbon dots fluorescence test solution or fluorescent test paper becomes brownish black by yellow, or is with wavelength
The ultraviolet light irradiation dropwise addition of 365nm has generation green fluorescence when the carbon dots fluorescence test solution or fluorescent test paper of solution to be measured to be quenched now
As detecting to contain ferric ion in solution to be measured；The color of carbon dots fluorescence test solution or fluorescent test paper is constant or green glimmering
Light is constant, that is, detects concentration < 1 μM in solution to be measured without ferric ion or ferric ion.
The method of the carbon dots fluorescence test solution or fluorescent test paper half-quantitative detection ferric ion is preferred are as follows: will be serial different
The concentration of volume is that the ferric ion stock solution of 1mg/mL is added drop-wise to respectively in the carbon dots fluorescence test solution of fixed concentration, makes carbon
The ultimate density of ferric ion is 1~100 μM of series standard solution in point fluorescence test solution, and records each series standard solution
Color；Solution to be measured is added drop-wise in the carbon dots fluorescence test solution for possessing above-mentioned fixed concentration, and with each series standard solution
Color is compared, and carries out the semi-quantitative analysis of ferric ion content in solution to be measured；
Or 1~100 μM of ferric ion solution is added drop-wise on fluorescent test paper and (preferably uses rubber head as a control group
1~100 μM of ferric ion solution is added dropwise 5 and dripped on respective fluorescent test paper by dropper), record the color of each control group；
Solution to be measured is added drop-wise on fluorescent test paper identical with control group, and is compared with the color of each control group, is carried out to be measured
The semi-quantitative analysis of ferric ion content in solution.It can be achieved<1 μM ,~20 μM ,~50 μM ,~80 μM,>100 μM five kinds dense
Spend the detection of rank.
The method of the carbon dots fluorescence test solution quantitative detection ferric ion is preferred are as follows: is with the fluorescence test solution of fixed concentration
Blank group tests its fluorescence intensity F0, then the ferric ion stock solution of the serial different volumes of addition is configured to serial difference
The standard test liquid of concentration C i measures fluorescence intensity Fi respectively；It is repeated 3 times test to be averaged, draws Ci~(Fi/F0) standard
Curve；
Ferric ion stock solution is replaced to measure fluorescence intensity Fx referring to above-mentioned process with solution to be measured, according to standard song
Line computation goes out the content Cx of ferric ion in solution to be measured.
Compared with the prior art, the advantages of the present invention are as follows: the present invention passes through one kettle way hydrothermal synthesis fluorescent carbon point, method
Simply, quickly, safely, and raw material is easy to get, is cheap；Fluorescence test solution or test paper obtained are high to the selectivity of metal ion,
Phenomenon is obvious, can be to Fe under naked eye3+It is quickly identified, and then can easily realize Fe3+Qualitative and semidefinite
The Glasslessization of amount detects；Fe can be also realized by means of general fluorescent sub-photometer3+Quantitative detection, sensitivity and inspection
It is excellent to survey limit；So fluorescent carbon point produced by the present invention has weight in the analysis of the actual samples such as environment, food, biology, medicine
Want meaning.
Detailed description of the invention
Fig. 1 is the uv absorption spectra and fluorescence spectra of carbon dots fluorescence test solution in the embodiment of the present invention 1；
Fig. 2 be the embodiment of the present invention 2 in the impregnated filter paper of carbon dots fluorescence test solution under fluorescent light with the figure under ultraviolet lamp；
Fig. 3 is Fe in the embodiment of the present invention 3~53+The test result figure of carbon dots fluorescence test solution and fluorescent test paper is quenched；
Fig. 4 is that the fluorescence intensity comparison after carbon dots fluorescence test solution is added in different metal ions solution in the embodiment of the present invention 6
Figure；
Fig. 5 is Fe in the embodiment of the present invention 63+To the influence diagram of the ultraviolet spectra of carbon dots fluorescence test solution；
Fig. 6 is the Fe of various concentration in the embodiment of the present invention 73+Fluorescence spectra and standard after carbon dots fluorescence test solution is added
Curve graph；
Fig. 7 is pH value in the embodiment of the present invention 12 to the influence diagram of carbon dots fluorescence test solution luminescent properties；
Fig. 8 is that carbon dots fluorescence test solution in pH value is the reversible fluorescence performance switched between 4 and 10 in the embodiment of the present invention 12
Figure.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
Embodiment 1:
Fluorescent carbon point solution the preparation method comprises the following steps: first by 0.5mL methacrylic acid (MAA) and 0.315g m-phenylene diamine (MPD)
(MPD) (molar ratio 2:1) is added in vial, and 10mL deionized water is added thereto, and stirring concussion solution is to admittedly
Body dissolution is complete；Again by (housing of hydrothermal reaction kettle is stainless steel material in the present embodiment, interior in solution importing hydrothermal reaction kettle
Set is polytetrafluoroethylene (PTFE) material, and polytetrafluoroethylene (PTFE) has superpower chemical stability, will not with solution reaction, stainless steel material it is outer
Set primarily serves high pressure resistant high temperature protection effect；Certainly, hydrothermal reaction kettle made of other materials can also be used)；Finally by water
Thermal response kettle is put into baking oven (temperature is 200 DEG C) heating reaction 3h, is cooled to room temperature, obtains clear brown clear solution；Most
Obtained clear brown clear solution is centrifuged 10min under conditions of 12000rpm afterwards, supernatant liquor is fluorescent carbon
Point solution；The ultraviolet-visible spectrogram and fluorescence of fluorescent carbon point solution are measured with ultraviolet specrophotometer and sepectrophotofluorometer
Spectrogram, as shown in Figure 1.
Fluorescent carbon point solution obtained above is put into and is freeze-dried to obtain fluorescent carbon in universal freeze drier
Point powder (certainly, if without freeze drier, also can be used vacuum oven is carried out under room temperature or low-grade fever state vacuum do
It is dry；Or it is dry directly under room temperature or low-grade fever state, only need longer drying time.But temperature when dry cannot
It is too high, otherwise will lead to carbon dots loss and two problems of reuniting), then being configured to mass-volume concentration with deionized water is 0.1g/L
Carbon dots fluorescence test solution.
Embodiment 2:
The preparation method is the same as that of Example 1 for carbon dots fluorescence test solution.
Carbon dots fluorescence test solution is drawn with pen, writes and draws a picture on paper.As shown in Fig. 2 (A) and 2 (B), carbon dots fluorescence
Test solution writing shows the yellow of carbon dots aqueous solution itself in the sunlight, and display is bright under ultraviolet light and clearly green fluorescence.
With folded filter paper at a little Hua, natural drying is taken out after immersing carbon dots fluorescence test solution.As shown in Fig. 2 (C) and 2 (D), by carbon dots
The paper flower that fluorescence test solution dyed is a flaxen paper flower in the sunlight, and it is glimmering to show bright green under ultraviolet light
Light.
Common commercially available round qualitative filter paper is cut into long 4cm, paper slip is put into carbon dots fluorescence by the rectangle paper slip of wide 0.7cm
In test solution, 2h is impregnated, further takes out to air-dry and detects Fe up to qualitative visualization3+Fluorescent test paper.
Embodiment 3:
Carbon dots fluorescence test solution obtained in above-described embodiment 1 is taken, is separately added into 13 small test tubes that number is 1~13
10mL, then 0.1mL blank solution (deionized water) and different metal ion solutions (concentration is 0.1M) to be measured are successively added dropwise
Into each small test tube, stand after sufficiently vibrating, shaking up to get multiple groups test solution.The color of test solution becomes in each small test tube of naked eye
Change situation, when the color of test solution becomes brownish black by yellow, i.e., known to contain Fe in the test solution3+, and then realize that qualitative detection waits for
Survey the Fe in solution3+.Shown in testing result such as Fig. 3 (A), small test tube is successively for number 1~13 from left to right: blank group, Cu2 +, Fe2+, Fe3+, Co2+, Pb2+, Cd2+, Cr3+, Ni2+, Mn2+, Ag+, Zn2+, Al3+。
Embodiment 4:
Multiple groups test solution made from above-described embodiment 3 is taken, is irradiated with hand-held ultraviolet lamp (wavelength 365nm), naked eye
The color change situation of test solution in each small test tube, when the green fluorescence of test solution is quenched, i.e., known to contain Fe in the test solution3+, in turn
Realize the Fe in qualitative detection solution to be measured3+.Shown in testing result such as Fig. 3 (B), small test tube from left to right number 1~13 according to
It is secondary to be: blank group, Cu2+, Fe2+, Fe3+, Co2+, Pb2+, Cd2+, Cr3+, Ni2+, Mn2+, Ag+, Zn2+, Al3+。
Embodiment 5:
Fluorescent test paper obtained in above-described embodiment 2 is taken, and fluorescent test paper is arranged successively and is come, then by blank solution
(deionized water) and different solution to be measured are successively added drop-wise on each fluorescent test paper, are shone with hand-held ultraviolet lamp (wavelength 365nm)
Penetrate, the color change situation of each fluorescent test paper of naked eye, when the green fluorescence of fluorescent test paper is quenched, i.e., known to be added drop-wise to this glimmering
Contain Fe in solution to be measured on light test paper3+, and then realize the Fe in qualitative detection solution to be measured3+.Testing result such as Fig. 3 (C)
Shown, fluorescent test paper is successively from left to right: blank group, Cu2+, Fe2+, Fe3+, Co2+, Pb2+, Cd2+, Cr3+, Ni2+, Mn2+, Ag+, Zn2+, Al3+。
Embodiment 6:
Multiple groups test solution made from above-described embodiment 3 is taken, with the fluorescence intensity of each test solution of fluorescence spectrophotometer measurement, blank
Solution is denoted as F0, other solution to be measured are denoted as F, with F/F0For ordinate, using each different samples as abscissa, mapping result
As shown in figure 4, showing Fe3+Have specific selectivity, it can be achieved that qualitative detection the quenching effect of carbon dots fluorescence test solution.
Fig. 5 is Fe3+To carbon dots ultra-violet absorption spectrum, carbon dots have an absorption peak (bent see CNs in figure at about 440nm
Line), Fe is added3+Later, which disappears (see CNs+Fe curve in figure).Thus infer, possible Fe3+With carbon dots knot
Conjunction forms special co-ordination complex, causes carbon dots not to be excited in excitation wave strong point, therefore result in the fluorescent quenching of carbon dots.
Embodiment 7:
It takes carbon dots fluorescence test solution made from above-described embodiment 1 as blank control group, tests its fluorescence intensity F0。
Using ferric trichloride as raw material, the ferric ion stock solution of 1mg/mL is configured, the carbon in above-mentioned fixed concentration is passed through
The ferric ion stock solution of different volumes is added in point fluorescence test solution, is prepared into the Fe of serial various concentration3+Standard solution (iron
The ultimate density of ion is respectively 1 μM, 10 μM, 20 μM, 40 μM, 60 μM, 80 μM, 100 μM).The fluorescence for measuring these solution is strong
Spend F.It repeatedly tests, carries out linear fit and obtain corresponding linear equation, related coefficient and minimum detectability, mapping is drawn
Standard curve is produced, as a result as shown in Figure 6.
When concrete application, the fluorescence intensity Fx of sample to be tested, the linear relationship then obtained according to Fig. 6 are first measured
Obtain the Fe of sample to be tested3+Concentration C x.
Embodiment 8:
Carbon dots fluorescence test solution the preparation method comprises the following steps: first by 0.5mL methacrylic acid (MAA) and 0.63g m-phenylene diamine (MPD)
(MPD) (molar ratio 1:1) is added in vial, and 7.5mL deionized water is added thereto, and stirring concussion solution is to admittedly
Body dissolution is complete；Solution is imported in hydrothermal reaction kettle again；Hydrothermal reaction kettle (temperature is 60 DEG C) is finally put into baking oven to add
Thermal response 5h, is cooled to room temperature, and obtains clear brown clear solution；Finally obtained clear brown clear solution is existed
Be centrifuged 5min under conditions of 10000rpm, supernatant liquor by freeze-drying, then re-dissolved with deionized water be configured to it is dense
Degree is the carbon dots fluorescence test solution of 0.3g/L.
Common commercially available round qualitative filter paper is cut into long 4cm, paper slip is put into above-mentioned carbon dots by the rectangle paper slip of wide 0.7cm
In fluorescence test solution, 0.5h is impregnated, naturally dry is further taken out up to qualitative visualization and detects Fe3+Fluorescent test paper.
After tested, the carbon dots fluorescence test solution of the present embodiment and fluorescent test paper are used equally for qualitative and quantitative detection solution to be measured
In Fe3+, and high sensitivity, phenomenon are obvious.
Embodiment 9:
Carbon dots fluorescence test solution the preparation method comprises the following steps: first by 0.75mL methacrylic acid (MAA) and 0.315g m-phenylene diamine (MPD)
(MPD) (molar ratio 3:1) is added in vial, and 22.5mL deionized water is added thereto, and stirring concussion solution is extremely
Solid dissolution is complete；Solution is imported in hydrothermal reaction kettle again；Hydrothermal reaction kettle is finally put into baking oven (temperature is 120 DEG C)
Heating reaction 0.5h, is cooled to room temperature, obtains clear brown clear solution；Finally obtained clear brown clear solution is existed
Be centrifuged 8min under conditions of 15000rpm, supernatant liquor by freeze-drying, then re-dissolved with deionized water be configured to it is dense
Degree is the carbon dots fluorescence test solution of 0.5g/L.
Common commercially available round qualitative filter paper is cut into long 4cm, paper slip is put into above-mentioned carbon dots by the rectangle paper slip of wide 0.7cm
In fluorescence test solution, 3h is impregnated, naturally dry is further taken out up to qualitative visualization and detects Fe3+Fluorescent test paper.
After tested, the carbon dots fluorescence test solution of the present embodiment and fluorescent test paper are used equally for qualitative and quantitative detection solution to be measured
In Fe3+, and high sensitivity, phenomenon are obvious.
Embodiment 10:
Take carbon dots fluorescence test solution made from above-described embodiment 8, be added different volumes concentration be 1mg/mL ferric iron from
Sub- stock solution is prepared into the Fe of serial various concentration3+Standard solution as a control group (ultimate density of iron ion is respectively 1 μM,
20 μM, 50 μM, 80 μM, 100 μM).Record the color of each control group；Then solution to be measured is added drop-wise to and control group same concentrations
Carbon dots fluorescence test solution in, and be compared with the color of each control group, probably containing for ferric ion in solution to be measured can be obtained
Amount, and then realize the semi-quantitative analysis of ferric ion content.
Embodiment 11:
Fluorescent test paper made from above-described embodiment 9 is taken, by the ferric ion standard solution (concentration point of serial known concentration
Wei not be 1 μM, 20 μM, 50 μM, 80 μM, 100 μM) it is dripped on above-mentioned fluorescent test paper as a control group with rubber head dropper dropwise addition 3 respectively,
Record the color of each control group；Then solution to be measured is added drop-wise in fluorescent test paper identical with control group, and with each control group
Color be compared, the approximate content of ferric ion in solution to be measured can be obtained, and then realize the half of ferric ion content
Quantitative analysis.
Embodiment 12:
Carbon dots fluorescence test solution made from above-described embodiment 8 is taken, influence of the pH value to carbon dots fluorescence test solution luminescent properties is measured,
Determine this method pH range applicable in actual sample measurement.As shown in fig. 7, fluorescence intensity maintains in the range of pH 2~9
Stablize；As pH >=10, fluorescence intensity is greatly lowered.Therefore, this method is three suitable for the actual sample of pH 2~9
The detection of valence iron ion.It, can be laggard by the way that the buffer adjusting of pH 2~9 is added for being unsatisfactory for the actual sample of this requirement
Row measurement.
In addition, the carbon dots fluorescence test solution is also used as detection of the pH sensor for medium pH.As shown in figure 8, pH is 4
And switch repeatedly between 10, the fluorescence intensity of the carbon dots fluorescence test solution also changes repeatedly, show pH adjust fluorescent characteristic and
The good fluorescence reversibility in acid and strong basicity environment.
Claims (7)
1. a kind of preparation method of fluorescent carbon point, it is characterised in that include the following steps: be with the methacrylic acid of an equivalent
Methacrylic acid and m-phenylene diamine (MPD) that molar ratio is 1~3:1 are dissolved in the deionized water of 15~30 times of equivalents by calculating benchmark,
Obtain solution A；Then solution A is transferred in hydrothermal reaction kettle, 60~200 DEG C are heated to after closed and is reacted, when reaction
Between 0.5~5 hour, cooled to room temperature, obtains solution B after reaction；Above-mentioned solution B is centrifuged, centrifugal rotational speed
10000~15000rpm, 5~10min of centrifugation time, gained supernatant liquor obtains carbon dots fluorescent powder by freeze-drying after centrifugation
End re-dissolves carbon dots fluorescent powder with deionized water, is prepared into the carbon dots fluorescence test solution of 0.1~0.5g/L.
2. carbon dots fluorescence test solution made from a kind of preparation method as described in claim 1 is in Visual retrieval ferric ion
Using.
3. application according to claim 2, it is characterised in that: filter paper is put into above-mentioned carbon dots fluorescence test solution and impregnates 0.5
It~3 hours, further takes out naturally dry or cold wind drying obtains fluorescent test paper.
4. application according to claim 3, it is characterised in that: the carbon dots fluorescence test solution or fluorescent test paper detect ferric iron
The method of ion includes qualitative detection, half-quantitative detection and quantitative detection.
5. application according to claim 4, it is characterised in that: the carbon dots fluorescence test solution or fluorescent test paper qualitative detection three
The method of valence iron ion are as follows: solution to be measured is added drop-wise in carbon dots fluorescence test solution or on fluorescent test paper, carbon dots fluorescence test solution or glimmering
The color of light test paper becomes brownish black by yellow, or the carbon dots for having solution to be measured are added dropwise in the ultraviolet light irradiation for being 365nm with wavelength
Green fluorescence quenching phenomenon occurs when fluorescence test solution or fluorescent test paper, that is, detects to contain ferric ion in solution to be measured；Carbon
The color of point fluorescence test solution or fluorescent test paper is constant or green fluorescence is constant, that is, detects in solution to be measured without ferric ion
Or concentration < 1 μM of ferric ion.
6. application according to claim 4, it is characterised in that: the carbon dots fluorescence test solution or fluorescent test paper half-quantitative detection
The method of ferric ion are as follows: be added drop-wise to the ferric ion stock solution that the concentration of serial different volumes is 1mg/mL respectively
In the carbon dots fluorescence test solution of fixed concentration, make 1~100 μM of ultimate density of series of ferric ion in carbon dots fluorescence test solution
Standard solution, and record the color of each series standard solution；Solution to be measured is added drop-wise to possess above-mentioned fixed concentration carbon dots it is glimmering
It in light test solution, and is compared with the color of each series standard solution, carries out the semidefinite of ferric ion content in solution to be measured
Amount analysis；
Or be added drop-wise to 1~100 μM of ferric ion standard solution on fluorescent test paper as a control group, record each control group
Color；Solution to be measured is added drop-wise on fluorescent test paper identical with control group, and is compared with the color of each control group, into
The semi-quantitative analysis of ferric ion content in row solution to be measured.
7. application according to claim 4, it is characterised in that: the carbon dots fluorescence test solution quantitative detection ferric ion
Method are as follows: test its fluorescence intensity F by blank group of the fluorescence test solution of fixed concentration0, the three of serial different volumes are then added
Valence iron ion stock solution is configured to the standard test liquid of serial various concentration Ci, measures fluorescence intensity Fi respectively；It is repeated 3 times examination
It tests and is averaged, draw Ci~(Fi/F0) standard curve；
Ferric ion stock solution is replaced to measure fluorescence intensity Fx referring to above-mentioned process with solution to be measured, according to standard curve meter
Calculate the content Cx of ferric ion in solution to be measured.
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