CN109777408B - A kind of high-fluorescence quantum yield N doping carbon dots and its preparation method and application - Google Patents
A kind of high-fluorescence quantum yield N doping carbon dots and its preparation method and application Download PDFInfo
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- CN109777408B CN109777408B CN201910135338.0A CN201910135338A CN109777408B CN 109777408 B CN109777408 B CN 109777408B CN 201910135338 A CN201910135338 A CN 201910135338A CN 109777408 B CN109777408 B CN 109777408B
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Abstract
The invention discloses a kind of high Day-Glo blue N doping carbon dots, it is nitrogen source by carbon source, amides compound of organic acid, carries out microwave treatment and is prepared.The present invention uses simple microwave synthesis process, and the preparation method being related to is simple, the reaction time is extremely short, and raw material dosage is few, source is wide, at low cost, is suitble to promote and apply；Gained N doping carbon dots fluorescence quantum yield is high, and excellent selectivity and sensitivity can be shown to silver ion, with important application prospects in the fields such as heavy metal water pollution and biological detection.
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to a kind of high-fluorescence quantum yield N doping carbon dots and its preparation side
Method and application.
Background technique
Serious harm in view of heavy metal ion to human health and environment, detection of heavy metal ion are increasingly becoming world's model
Enclose an interior major issue.Recently, silver be used as a kind of Heavy Metals, be used as decoration and material be widely used in electronics,
The industries such as medicine.However, recent research indicate that the antibacterial activity of Nano silver grain may be attributed to toxic silver ion, silver ion
It has been classified as one of most highly toxic heavy metal ion.
Currently, Silver detection technology mainly includes atomic absorption spectrum (AAS), inductivity coupled plasma mass spectrometry
(ICP-MS), inductively coupled plasma atomic emission (ICP-OES), Surface enhanced Raman scattering, Flow Injection Analysis and molten
Voltammetry etc. out.Though these detection techniques sensibility with higher and selectivity, usually require cumbersome sample preparation and
Preconcentration procedure, and need to be equipped with expensive instrument and professional, it is not suitable for use in setting with the portable of site inspection in real time
It is standby.In contrast, fluorescence sense detection technique has very high potentiality, can high-throughput detection scene Ag+Ion.
In addition, the fast development of nanotechnology provides new performance machine for the sensitivity of fluorescent optical sensor and selectivity
Meeting.The variation of the physicochemical properties for the fluorogen that fluorescence sense is induced based on analyte, for example, fluorescence intensity, the service life and respectively to
The opposite sex, it is related with electric charge transfer or energy transfer process.However, having been reported compared with other metal-ion fluorescent sensors
Relatively small number of Ag+Ion fluorescence sensor.Currently, most of fluorescent optical sensors for Ag ion exist, toxicity is big, gives birth to
Object poor compatibility detects the disadvantages of poor specificity, synthesis technology are complicated, preparation cost is expensive, by-product is more: as existing nitrogen is mixed
Miscellaneous or nitrogen sulfur doping carbon dots be chiefly used in detect biological thiol, and the fluorescence probe for detecting silver ion it is relatively fewer (such as Zhang S,
LinB,Yu Y,et al.A ratiometric nanoprobe based on silver nanoclusters and
carbon dots for the fluorescent detection of biothiols[J]
.SpectrochimicaActaPartA:Molecular andBiomolecular Spectroscopy,2018,195:230-
235)；For detecting the N doping of silver ion or nitrogen sulfur doping carbon dots while also can detect mercury ion, poor specificity (such as Onepot
synthesis of highly fluorescent N doped C-dots and used as fluorescent probe
detection for Hg2+,and Ag+,in aqueous solution[J].Sensors&ActuatorsB Chemical,
2017,243:244-253) a small number of probes that can be used for specificity detection silver ion, mostly use hydrothermal synthesis, not only the reaction time
Long and raw material was held high, by-product it is more (such as " a kind of preparation method for detecting the carbon dots of silver ion and dimercaptosuccinic acid and its
Using ") by-product more need multi-step impurity removal step, it is not easy to operate.
Therefore, the Silver detection technology for further developing green, cheap, simplicity and Efficient robust, has important grind
Study carefully and application value.
Summary of the invention
It is a primary object of the present invention to mix in view of the deficienciess of the prior art, providing a kind of high-fluorescence quantum yield nitrogen
Miscellaneous carbon dots are, it can be achieved that heavy metal Ag+Easy, efficient trace detection, and the preparation method being related to is simple, generated time is extremely short,
One new thought can be provided for detection of heavy metal ion technology.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of high-fluorescence quantum yield N doping carbon dots, preparation method include the following steps:
1) citric acid and glutamine are ground uniformly, obtains mixed-powder；
2) mixed-powder is subjected to microwave treatment, obtains precursor solution；
3) under agitation, gained precursor solution is added dropwise in lye and adjust gained mixed system pH value to
Neutrality is cooled to room temperature, and obtains suspension；
4) gained suspension is filtered, obtains N doping carbon dots solution.
In above scheme, the mass ratio of the citric acid and glutamine is 1:(0.1~0.5).
In above scheme, the microwave treatment power is 750~950W, and the time is 3~10min.
In above scheme, the pH value of lye described in step 3) is 9.8~10.5.
In above scheme, sodium hydroxide solution, potassium hydroxide solution or sodium bicarbonate solution etc. is can be selected in the lye.
In above scheme, the volume ratio of the precursor solution and lye is 1:(15~20).
In above scheme, the filtration step is 0.22 μm of microfiltration membranes.
According to N doping carbon dots prepared by above scheme, fluorescent yield may be up to 22%, be applied to complicated water sample
Middle heavy metal Ag+Trace detection can express excellent silver ion selective and sensitivity.
The principle of the present invention are as follows:
The present invention is nitrogen source by carbon source, glutamine of citric acid, synthesizes nitrogen-doped carbon point using microwave synthesis process, leads to
Sodium hydrate regulator solution pH value is crossed to obtain high yield blue-fluorescence carbon dots；Amino that gained carbon dots surface is rich in, carboxyl and
The functional groups such as hydroxyl can be with Ag+It is combined by force and faster sequestration, promotes the non-radiative recombination of exciton by electronic transfer process,
Excellent selectivity and sensitivity are shown to silver ion.
Compared with prior art, the invention has the benefit that
1) N doping carbon dots of the present invention use simple microwave synthesis process, and the preparation method being related to is simple, reacts
Time is extremely short, and raw material dosage is few, at low cost, is suitble to promote and apply.
2) gained N doping carbon dots fluorescence quantum yield is high, and excellent selectivity and sensitive can be shown to silver ion
Property, it is with important application prospects in the fields such as heavy metal water pollution and biological detection.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of 1 gained N doping carbon dots of the embodiment of the present invention.
Fig. 2 is (a) C of 1 gained N doping carbon dots of the embodiment of the present invention1sSwarming map；(b)N1sSwarming map；(c)O1s
Swarming map.
Fig. 3 is (a) ultraviolet spectrogram of 1 gained N doping carbon dots of the embodiment of the present invention；(b) fluorescence excitation map and fluorescence
Emit map；(c) the transmitting map under different fluorescence exciting wavelengths.
Fig. 4 is 2 gained N doping carbon dots of embodiment of the present invention fluorescence intensity change curve at different pH.
Fig. 5 is 2 gained N doping carbon dots of embodiment of the present invention fluorescence intensity change curve in various concentration NaCl.
Fig. 6 is 40 μM of Ag+With 400 μM of other metal ions to N doping carbon dots fluorescent quenching degree, show the nitrogen of preparation
Carbon dots are adulterated to Ag+Detection has highly selective.
Fig. 7 is various concentration Ag+It is added to the fluorescence intensity change after the N doping carbon dots of preparation.
Fig. 8 is fluorescence intensity change and Ag+The linear relationship of concentration shows that 0- may be implemented in the N doping carbon dots of preparation
To heavy metal Ag within the scope of 500 μM+Detection.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of high-fluorescence quantum yield N doping carbon dots, preparation method include the following steps:
1) 1g monohydrate potassium and 0.2g D-Gln are placed in mixing in agate mortar to grind well, obtain mixed-powder；
2) gained mixed-powder is placed in 750W household microwave oven and heats 5min, obtain precursor solution；
3) under the conditions of magnetic agitation, gained 2mL precursor solution is added in 30mL 0.008g/L sodium hydroxide solution
(pH10.5) and continue to adjust pH to 7 with sodium hydroxide, subsequent cooled to room temperature obtains suspension；
4) gained suspension is filtered with 0.22 μm of microfiltration membranes, collects filtered solution to get high-fluorescence quantum yield nitrogen
Adulterate carbon dots solution.
Fig. 1 is the transmission electron microscope picture of N doping carbon dots obtained by the present embodiment, and the size of gained N doping carbon dots is shown in figure
Between 5-9nm.
Fig. 2 (a), 2 (b), 2 (c) are respectively the C of N doping carbon dots manufactured in the present embodiment1s、N1s、O1sSwarming map, can
To find out that products therefrom is successfully realized N doping.
Fig. 3 (a) is the ultraviolet spectrogram of N doping carbon dots obtained by the present embodiment, it can be seen that N doping carbon dots are in 334nm
There is strong fluorescence at place；Fig. 3 (b), Fig. 3 (c) be respectively N doping carbon dots obtained by the embodiment of the present invention fluorescence excitation map and
Transmitting map under fluorescent emission map, different fluorescence exciting wavelengths, excitation wavelength is that 340nm has most by force as can be seen from Fig.
Fluorescence intensity, fluorescence emission spectrum peak position is set to 430nm.
Embodiment 2
A kind of high-fluorescence quantum yield N doping carbon dots, preparation method include the following steps:
1) 1g monohydrate potassium and 0.2g D-Gln are mixed in agate mortar and is ground well, obtain mixed-powder；
2) gained mixed-powder sample is placed in 950W household microwave oven and heats 10min, obtain precursor solution；
3) under the conditions of magnetic agitation, 30mL 0.008g/L sodium hydroxide solution is added in 2mL precursor solution (pH is
10.5) pH to 7 is adjusted in and with sodium hydroxide, subsequent cooled to room temperature obtains suspension；
4) by 0.22 μm of micro-filtrate membrane filtration of suspension, filtered solution is collected to get high-fluorescence quantum yield N doping carbon dots
Solution.
After tested, the fluorescence intensity under the irradiation of 340nm light of N doping carbon dots obtained by the present embodiment is 1232a.u..
Fig. 4 is N doping carbon dots fluorescence intensity change curve at different pH obtained by the present embodiment, as seen from the figure, gained
Higher fluorescence intensity can be obtained when the pH of carbon dots solution is greater than 6.36.
Fig. 5 is N doping carbon dots fluorescence intensity change curve in various concentration NaCl obtained by embodiment, as seen from the figure
Fluorescence intensity is still unaffected especially in high concentration NaCl solution (2.5M) for gained N doping carbon dots of the invention.
Embodiment 3
A kind of high-fluorescence quantum yield N doping carbon dots, preparation method include the following steps:
1) 1g monohydrate potassium and 0.4g D-Gln are mixed in agate mortar and is ground well, obtain mixed-powder；
2) gained mixed-powder sample is placed in 950W household microwave oven and heats 8min, obtain precursor solution；
3) under the conditions of magnetic agitation, 40mL 0.008g/L sodium hydroxide solution is added in 2mL precursor solution (pH is
10.5) pH to 7 is adjusted in and with sodium hydroxide, subsequent cooled to room temperature obtains suspension；
4) by 0.22 μm of micro-filtrate membrane filtration of suspension, filtered solution is collected to get high-fluorescence quantum yield N doping carbon dots
Solution.
After tested, the fluorescence intensity under the irradiation of 340nm light of N doping carbon dots obtained by the present embodiment is 701a.u..
Application examples 1
2 gained N doping carbon dots of the embodiment of the present invention are applied to heavy metal Ag+Detection, specific steps include the following: to take
100 μ L N doping carbon dots spend ionized water and are diluted to 1mL, and it is F that fluorescence intensity is recorded under the excitation wavelength of 340nm0；It is another respectively
Take 100 μ L N doping carbon dots, 100 μ L, 40 μM of Ag+, 400 μM of other metal ions (Co2+、Cu2+、Mn2+Deng) to N doping carbon dots
Fluorescent quenching degree.
Fig. 6 is respectively 40 μM of Ag+With 400 μM of other metal ions to N doping carbon dots fluorescent quenching curve, show this hair
Bright gained N doping carbon dots are to Ag+Detection has highly selective.
Application examples 2
2 gained N doping carbon dots of the embodiment of the present invention are applied to heavy metal Ag+Detection, specific steps include the following: to take
100 μ L N doping carbon dots spend ionized water and are diluted to 1mL, and it is F0 that fluorescence intensity is recorded under the excitation wavelength of 340nm；Separately take
100 μ L N doping carbon dots, 100 μ L various concentration Ag+Solution is then diluted to 1mL with deionized water, records its fluorescence intensity and is
F, (F0-F)/F0 are Ag+Detect signal.
Fig. 7 is various concentration Ag+It is added to the fluorescence intensity change after N doping carbon dots solution；Fig. 8 is fluorescence intensity change
Change and Ag+The linear relationship of concentration；Test result shows that gained N doping carbon dots of the invention may be implemented within the scope of 0-500 μM
To heavy metal Ag+Detection is, it can be achieved that Ag+Highly sensitive detection.
Comparative example
This comparative example is attempted by carbon source, glutamine of benzoic acid to be nitrogen source, synthesizes N doping using microwave synthesis process
Carbon dots specifically comprise the following steps:
1) 0.7g benzoic acid and 0.4g D-Gln are mixed in agate mortar and is ground well, obtain mixed-powder；
2) gained mixed-powder sample is placed in 950W household microwave oven and heats 5min, obtain precursor solution；
3) 20mL 0.008g/L sodium hydroxide solution (pH under the conditions of magnetic agitation, is added in 1.5mL precursor solution
To adjust pH to 7 in 10.5) and with sodium hydroxide, subsequent cooled to room temperature obtains suspension；
4) by 0.22 μm of micro-filtrate membrane filtration of suspension, filtered solution is collected；
5) the 500 above-mentioned filtered solutions of μ L are taken to be diluted to 1mL with deionized water, fluorescence intensity is under the excitation wavelength of 340nm
108a.u.；The 500 above-mentioned filtered solutions of μ L are separately taken, 100 μ L, 100 μM of Ag are added+With 800 μ L deionized waters, in the excitation wave of 340nm
Fluorescence intensity is 106a.u. after tested under length.
The above results show: the carbon dots using benzoic acid with D-Gln as primary raw material by microwave process for synthesizing formation are glimmering
It light low yield and cannot achieve to Ag+Efficient detection.
Each raw material cited by the present invention can realize that the bound value of the present invention and each raw material, interval value can
Realize the present invention；Embodiment numerous to list herein.The bound value of technological parameter of the invention, interval value can realize this
Invention, embodiment numerous to list herein.
Claims (9)
1. a kind of preparation method of high-fluorescence quantum yield N doping carbon dots, which comprises the steps of:
1) citric acid and glutamine are ground uniformly, obtains mixed-powder；
2) mixed-powder is subjected to microwave treatment, obtains precursor solution；
3) under agitation, gained precursor solution is added dropwise in lye and adjusts the pH value of gained mixed system into
Property, it is cooled to room temperature, obtains suspension；
4) gained suspension is filtered, obtains N doping carbon dots solution.
2. preparation method according to claim 1, which is characterized in that the mass ratio of the citric acid and glutamine is 1:
(0.1~0.5).
3. preparation method according to claim 1, which is characterized in that the microwave treatment power is 750~950W, time
For 3~10min.
4. preparation method according to claim 1, which is characterized in that the pH value of lye described in step 3) be 9.8~
10.5。
5. preparation method according to claim 1, which is characterized in that the lye is sodium hydroxide solution, potassium hydroxide
Solution or sodium bicarbonate solution.
6. preparation method according to claim 1, which is characterized in that the volume ratio of the precursor solution and lye is 1:
(15~20).
7. preparation method according to claim 1, which is characterized in that the filtration step uses 0.22 μm of microfiltration membranes.
8. the high-fluorescence quantum yield N doping carbon dots of any one of the claim 1~7 preparation method preparation.
9. application of the high-fluorescence quantum yield N doping carbon dots in Silver detection field described in claim 8.
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