CN108251108A - A kind of preparation of iron ion doping carbon quantum dot and obtained carbon quantum dot and application - Google Patents
A kind of preparation of iron ion doping carbon quantum dot and obtained carbon quantum dot and application Download PDFInfo
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- CN108251108A CN108251108A CN201810065962.3A CN201810065962A CN108251108A CN 108251108 A CN108251108 A CN 108251108A CN 201810065962 A CN201810065962 A CN 201810065962A CN 108251108 A CN108251108 A CN 108251108A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—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
Abstract
Preparation and obtained carbon quantum dot and application the invention discloses a kind of iron ion doping carbon quantum dot, wherein, carbon source, nitrogen source and source of iron are scattered in organic solvent, solvent thermal reaction is carried out, obtains the iron ion doping carbon quantum dot；Wherein, the preparation method is simple, and organic reaction is carried out without introducing complicated functional group, and is only simple Hybrid Heating reaction, suitable for commercial Application；Also, obtained iron ion doping carbon quantum dot has very high fluorescence quantum yield, reaches as high as 97.8%；Meanwhile fluorescence property is good in organic solvent for iron ion doping carbon quantum dot, but fluorescence intensity is to have significantly to be quenched after a small amount of water is added in, therefore available for the detection of Water in Organic Solvents content, detection limit can be to 0.01%.
Description
Technical field
The present invention relates to nano-luminescent material field more particularly to carbon quantum dots, particularly, are related to iron ion doping carbon amounts
The preparation of son point and obtained carbon quantum and application.
Background technology
With the fast development of nanometer technology, novel nano fluorescent material prepares simple, resistance to photobleaching, sensitivity with it
The high, advantages such as dynamic range is wide and be widely used in the fields such as cell marking, cell imaging, medical diagnosis, analysis detection.Newly
Type nano-luminescent material mainly includes two major class：Semiconductor-quantum-point and carbon quantum dot, wherein carbon quantum dot have and semiconductor
The similar fluorescence property of quantum dot, at the same also have the toxicity that does not have of semiconductor-quantum-point low and good biocompatibility it is excellent
Point, therefore receive significant attention.
Carbon quantum dot refers to the carbon spherical nano particle as main component smaller in seize than 10nm.It cuts
Only at present, it is each using different carbon simple substance and organic matter as presoma to have prepared performance using different preparation methods by researcher
Different fluorescent carbon quantum dot.Theoretically, as long as can serve as the presoma of carbon quantum dot containing carbon, coal, apple, tree
Leaf, hair, flour, egg shell membrane, soya-bean milk, fruit juice etc. may be incorporated for preparing carbon quantum dot.The preparation method of carbon quantum dot is main
Including " from top to bottom " and " from bottom to top " two methods.So-called " from top to bottom " method refers to bulk carbon material passing through electric arc
The methods of cutting, laser ablation, is broken into the carbon material of below 10nm；And " from bottom to top " rule is to choose different small sizes
Presoma, through the carbon nano-particle for chemically reacting slowly long below great achievement 10nm.
But in existing preparation method, the problem of quantum yield of generally existing carbon quantum dot is low, this is in certain journey
The application of carbon quantum dot is limited on degree.
Invention content
In order to overcome the above problem, present inventor has performed sharp study, using carbon source, nitrogen source and source of iron in organic solvent
Middle reaction, obtains a kind of iron ion doping carbon quantum dot, and there is the iron ion doping carbon quantum size uniformity, fluorescent quantum to produce
The advantages of rate height (reaching as high as 97.8%), also, fluorescence property is good in organic solvent for the iron ion doping carbon quantum dot
It is good, but fluorescence intensity is to have significantly to be quenched, therefore available for the detection of Water in Organic Solvents content after a small amount of water is added in, thus
Complete the present invention.
One of the objects of the present invention is to provide a kind of preparations of iron ion doping carbon quantum dot, are embodied in following several
A aspect：
(1) a kind of preparation method of iron ion doping carbon quantum dot, wherein, it the described method comprises the following steps：
Step 1 adds in carbon source, nitrogen source and source of iron in organic solvent, forms precursor solution；
Precursor solution described in step 1 is placed in reaction kettle by step 2, is reacted, preferably cooled down after reaction；
Step 3 is post-processed, and obtains iron ion doping carbon quantum dot.
(2) preparation method according to above-mentioned (1), wherein, in step 1, the carbon source is selected from having for carbon elements
Machine object；Preferably, the carbon source is selected from the organic matter containing-COOH and/or-COONa, such as the organic matter containing-COONa；More
Preferably, the carbon source is selected from one or more of sodium citrate, citric acid, oxalic acid and sodium oxalate, such as sodium citrate.
(3) preparation method according to above-mentioned (1) or (2), wherein, in step 1, the nitrogen source is selected from Nitrogen element
Organic matter, be preferably selected from ethylenediamine and/or urea, such as urea.
(4) preparation method according to one of above-mentioned (1) to (3), wherein, in step 1, the source of iron be selected from iron from
Alite class is preferably selected from one or more of iron chloride, ferric sulfate, ferric nitrate and ferric acetate, such as iron chloride.
(5) preparation method according to one of above-mentioned (1) to (4), wherein, in step 1, the organic solvent is selected from
One or more of benzene,toluene,xylene, ethyl alcohol, tetrahydrofuran and carbon tetrachloride are preferably selected from benzene, toluene and dimethylbenzene
One or more of, such as toluene.
(6) preparation method according to one of above-mentioned (1) to (5), wherein, in the precursor solution,
The molar concentration of the carbon source is 0.01-10mol/L, more preferably preferably 0.01-1mol/L, 0.05-
0.5mol/L, such as 0.05~0.2mol/L；And/or
The molar concentration of the nitrogen source is 0.01-10mol/L, more preferably preferably 0.02-2mol/L, 0.05-
0.5mol/L, such as 0.1~0.3mol/L；And/or
The molar concentration of the source of iron is 0.05-10mol/L, more preferably preferably 0.05-0.5mol/L, 0.05-
0.2mol/L, such as 0.1mol/L；
Wherein, the molar concentration of source of iron is with the molar concentration meter of wherein ferro element.
(7) preparation method according to one of above-mentioned (1) to (6), wherein,
In step 2, the reaction is following carries out：5~50h is carried out at 100~500 DEG C, is preferable over 150~300 DEG C
Lower progress 8~for 24 hours, 10~14h, such as 200 DEG C of reaction 12h are carried out more preferably at 180~220 DEG C；And/or
In step 3, the post processing includes separation and drying, it is preferable that the separation was detached using cylindrical membrane
Filter or centrifugal process are detached, it is highly preferred that the drying is vacuum freeze drying or vacuum and heating drying, such as vacuum
Freeze-drying.
The second object of the present invention is to provide a kind of iron ion doping carbon quantum dot, is embodied in following side
Face：
(8) a kind of iron ion doping carbon quantum dot, it is preferred to use it is prepared by above-mentioned (1) to one of (7) the method, wherein,
The average grain diameter of the iron ion doping carbon quantum dot is 2~10nm, preferably 2~8nm；And/or
The fluorescence quantum yield of the iron ion doping carbon quantum dot is more than 90%, such as 97.8%；And/or
The iron ion doping carbon quantum dot sends out orange-yellow fluorescence under ultraviolet excitation.
One of the objects of the present invention is to provide a kind of application of the iron ion doping carbon quantum dot, be embodied in
Under several aspects：
(9) described in the iron ion doping carbon quantum dot obtained according to above-mentioned (1) to one of (7) the method or above-mentioned (8)
As fluorescence probe, analysis detection is carried out to the water content in organic solvent for the application of iron ion doping carbon quantum dot.
(10) application according to above-mentioned (9), wherein, the iron ion doping carbon quantum dot contains Water in Organic Solvents
The detection limit of amount is up to 0.01%.
Description of the drawings
Fig. 1 shows the transmission electron microscope picture of iron ion doping carbon quantum dot prepared by embodiment 1；
The three-dimensional fluorescence spectrogram and correspondence of the iron ion doping carbon quantum dot of the preparation of embodiment 1 is shown respectively in Fig. 2 a~Fig. 2 b
Colored spectrogram；
Fig. 2 c show that iron ion doping carbon quantum dot prepared by embodiment 1 is (right in natural light (left side) and 365nm wavelength
Side) ultraviolet light under fluorescent emission picture；
The three-dimensional fluorescence spectrogram and correspondence of the non-iron-doped iron carbon quantum dot of the preparation of comparative example 1 is shown respectively in Fig. 3 a~Fig. 3 b
Colored spectrogram；
Fig. 3 c show that non-iron-doped iron carbon quantum dot prepared by comparative example 1 is (right in natural light (left side) and 365nm wavelength
Side) ultraviolet light under fluorescent emission picture；
The three-dimensional fluorescence spectrogram and correspondence of the iron ion doping carbon quantum dot of the preparation of comparative example 2 is shown respectively in Fig. 4 a~Fig. 4 b
Colored spectrogram；
Fig. 4 c show that iron ion doping carbon quantum dot prepared by comparative example 2 is (right in natural light (left side) and 365nm wavelength
Side) ultraviolet light under fluorescent emission picture；
Fig. 5 shows the XPS spectrum figure of iron ion doping carbon quantum dot prepared by embodiment 1；
The fluorescent quantum production of carbon quantum dot prepared by embodiment 1, comparative example 1 and comparative example 2 is shown respectively in Fig. 6 a~Fig. 6 c
Rate calculates figure；
Fig. 7 shows 565nm in the acetonitrile solution that iron ion doping carbon quantum dot prepared by embodiment 1 is 10% in water content
Change with time the intensity (440nm excitations) of the fluorescence of place's transmitting figure；
Fig. 8 shows fluorescence spectrum of the iron ion doping carbon quantum dot of the preparation of embodiment 1 in the acetonitrile of different moisture content
Figure；
Fig. 9 shows two-dimentional correspondence figure of the fluorescent quenching from different water contents；
Figure 10 shows the standard curve of water content in iron ion doping carbon quantum dot detection acetonitrile prepared by embodiment 1.
Specific embodiment
Below by embodiment and experimental example, the present invention is described in more detail.Pass through these explanations, spy of the invention
Point and advantage will become more apparent from clearly.
First aspect present invention provides a kind of preparation method of iron ion doping carbon quantum dot, and the method includes following steps
Suddenly：
Step 1 adds in carbon source, nitrogen source and source of iron in organic solvent, forms precursor solution.
According to a kind of preferred embodiment of the present invention, in step 1, the carbon source is selected from the organic matter of carbon elements.
In further preferred embodiment, in step 1, the carbon source is selected from containing-COOH and/or-COONa
Organic matter, such as the organic matter containing-COONa.
In embodiment still more preferably, in step 1, the carbon source is selected from sodium citrate, citric acid, oxalic acid
One or more of with sodium oxalate, such as sodium citrate.
Wherein, using carbon source as primary raw material, carbon quantum dot is formed using " from bottom to top " method.Inventor passes through many experiments
It was found that the organic matter effect containing-COOH and/or-COONa is more preferable, the organic matter effect of further preferably-COONa is best.
According to a kind of preferred embodiment of the present invention, in step 1, the nitrogen source is selected from the organic matter of Nitrogen element.
In further preferred embodiment, in step 1, the nitrogen source is selected from ethylenediamine and/or urea, such as urinates
Element.
Wherein, the nitrogen source provides nitrogen for the formation of carbon quantum dot.
According to a kind of preferred embodiment of the present invention, in step 1, the source of iron is selected from iron ion salt.
In further preferred embodiment, in step 1, the source of iron be selected from iron chloride, ferric sulfate, ferric nitrate and
One or more of ferric acetate, such as iron chloride.
Wherein, inventor has found that the carbon quantum dot that preparation is doped using iron ion can be apparent by many experiments
Improve the fluorescence quantum yield of carbon quantum dot.Wherein, the fluorescence quantum yield of iron ion doping carbon quantum dot of the present invention can
To reach 97.8%.Also, obtained iron ion doping carbon quantum dot can steadily emit yellow light, and carbon amounts of the prior art
Son point generally all emits blue light, and still, blue light is not eye-catching, especially when being applied on biology, the cell tissue sheet in cell imaging
Body blue light-emitting, in this way, being difficult to distinguish.
According to a kind of preferred embodiment of the present invention, the organic solvent is selected from benzene,toluene,xylene, ethyl alcohol, tetrahydrochysene
One or more of furans and carbon tetrachloride.
In further preferred embodiment, the one kind or several of the organic solvent in benzene, toluene and dimethylbenzene
Kind.
In embodiment still more preferably, the organic solvent is toluene.
Wherein, in the present invention, using organic solvent as dicyandiamide solution, solvent thermal reaction is carried out, also, after the completion of reaction
The organic solvent of use can be recycled recycling.
Inventor has found that (1) has higher fluorescence volume compared to hydro-thermal method, the method for the invention by many experiments
Sub- yield, reaches 97.8%；(2) compared to hydro-thermal method, the iron ion that the method for the invention obtains is more suitable for answering commercial Application,
The industries such as weaving are advantageously used for, because obtained carbon quantum dot has better compatibility, industrially application range is wider.
According to a kind of preferred embodiment of the present invention, in the precursor solution, the molar concentration of the carbon source is
0.01-10mol/L。
In further preferred embodiment, in the precursor solution, the molar concentration of the carbon source is 0.01-
1mol/L。
In embodiment still more preferably, in the precursor solution, the molar concentration of the carbon source is
0.05-0.5mol/L, such as 0.05~0.2mol/L.
Wherein, the molar concentration of the carbon source is with the molar concentration meter of carbon source molecule.
According to a kind of preferred embodiment of the present invention, in the precursor solution, the molar concentration of the nitrogen source is
0.01-10mol/L。
In further preferred embodiment, in the precursor solution, the molar concentration of the nitrogen source is 0.02-
2mol/L。
In embodiment still more preferably, in the precursor solution, the molar concentration of the nitrogen source is
0.05-0.5mol/L, such as 0.1~0.3mol/L.
Wherein, the molar concentration of the nitrogen source is with the molar concentration meter of nitrogen source molecule.
According in an of the invention step preferred embodiment, in the precursor solution, the molar concentration of the source of iron
For 0.05-10mol/L.
In further preferred embodiment, in the precursor solution, the molar concentration of the source of iron is 0.05-
0.5mol/L。
In embodiment still more preferably, in the precursor solution, the molar concentration of the source of iron is
0.05-0.2mol/L, such as 0.1mol/L.
Wherein, the molar concentration of source of iron is found with the molar concentration meter of wherein ferro element, inventor by many experiments, with
The increase of Fe2O3 doping amount, fluorescence property enhancing still, continues with the increase of Fe2O3 doping amount, fluorescence property will not be into one
Step enhancing, therefore, inventor limits above-mentioned dosage.
Precursor solution described in step 1 is placed in reaction kettle by step 2, is reacted, preferably cooled down after reaction.
According to a kind of preferred embodiment of the present invention, in step 2, the reaction is following to be carried out：In 100~500 DEG C
5~50h of lower progress.
In further preferred embodiment, in step 2, the reaction is following to be carried out：At 150~300 DEG C into
Row 8~for 24 hours.
In embodiment still more preferably, in step 2, the reaction is following to be carried out：At 180~220 DEG C
Carry out 10~14h, such as 200 DEG C of reaction 12h.
According in a kind of preferred embodiment of the present invention, in step 2, natural cooling is preferably carried out after reaction.
Step 3 is post-processed, and obtains iron ion doping carbon quantum dot.
According to a kind of preferred embodiment of the present invention, in step 3, the post processing includes detaching and drying.
In further preferred embodiment, the separation is carried out using cylindrical membrane separator-filter or centrifugal process
Separation.
In embodiment still more preferably, the drying be vacuum freeze drying or vacuum and heating drying, preferably
Vacuum freeze drying.
Another aspect of the present invention discloses the iron ion doping that a kind of preparation method described according to a first aspect of the present invention obtains
Carbon quantum dot.
According to a kind of preferred embodiment of the present invention, the average grain diameter of the iron ion doping carbon quantum dot for 2~
10nm。
In further preferred embodiment, the average grain diameter of the iron ion doping carbon quantum dot is 2~8nm.
According to a kind of preferred embodiment of the present invention, the fluorescence quantum yield of the iron ion doping carbon quantum dot is
More than 90%.
In further preferred embodiment, the fluorescence quantum yield of the iron ion doping carbon quantum dot for 95% with
On, such as 97.8%.
Wherein, it is produced using the iron ion doping carbon quantum dot that the method for the invention obtains with very high fluorescent quantum
Rate reaches more than 90%, especially more than 95%, reaches as high as 97.8%.But in the prior art, the carbon quantum dot
Fluorescence quantum yield be generally 10% or so, increase even by the fluorescence quantum yield after other element dopings,
Also it is only capable of reaching 30%.
According to a kind of preferred embodiment of the present invention, the iron ion doping carbon quantum dot is sent out under ultraviolet excitation
Orange-yellow fluorescence.
Wherein, iron ion doping carbon quantum dot of the present invention has higher orange-yellow fluorescence intensity, this is significantly different
In general carbon quantum dot, carbon quantum dot described in the prior art sends out blue light under ultraviolet light, illustrates institute of the present invention again
It states iron ion doping carbon quantum dot and differs markedly from carbon quantum dot described in the prior art.
Third aspect present invention provides iron ion doping made from a kind of preparation method described according to a first aspect of the present invention
The application of iron ion doping carbon quantum dot described in carbon quantum dot or second aspect of the present invention.
According to a kind of preferred embodiment of the present invention, the iron ion doping carbon quantum dot is used as fluorescence probe, to having
Water content in solvent carries out analysis detection.
Wherein, inventor has found that fluorescence property is good in organic solvent for iron ion doping carbon quantum dot of the present invention,
But fluorescence intensity has and is significantly quenched after a small amount of water is added in, therefore available for the detection of Water in Organic Solvents content.
In further preferred embodiment, inspection of the iron ion doping carbon quantum dot to Water in Organic Solvents content
Limit is surveyed up to 0.01%.
Wherein, iron ion doping carbon quantum dot of the present invention reaches very low to the detection limit of Water in Organic Solvents content,
It can realize the detection of organic solvent analysis level.Also, it, which is successfully used for ethyl alcohol, acetonitrile, tetrahydrofuran, dioxane etc., has
The detection of water content in solvent, detection limit is up to 0.01%.
Advantageous effect includes possessed by the present invention：
(1) preparation method of the present invention is simple, and organic reaction is carried out without introducing complicated functional group, and is only simple
Hybrid Heating reaction, suitable for commercial Application；
(2) for preparation method of the present invention when applied to commercial Application, organic solvent can be recycled profit again
With；
(3) iron ion doping carbon quantum dot of the present invention has smaller grain size, and average grain diameter is 2~10nm；
(4) iron ion doping carbon quantum dot of the present invention has very high fluorescence quantum yield, reaches more than 90%,
Especially more than 95%, such as 97.8%, this is significantly unlike the prior art；
(5) iron ion doping carbon quantum dot of the present invention sends out orange-yellow fluorescence under ultraviolet light；
(6) iron ion doping carbon quantum dot of the present invention may be used as fluorescence probe, to the water content in organic solvent
Analysis detection is carried out, detection limit realizes the analysis level detection of organic solvent up to 0.01%.
Embodiment
The present invention is further described below by way of specific embodiment.But these embodiments are only exemplary, not
Any restrictions are formed to protection scope of the present invention.
Embodiment 1
0.5882g sodium citrates, 0.2404g urea, 0.3233g iron chloride and the mixing of 20mL toluene are taken, forms presoma
Solution；
Obtained precursor solution is placed in the stainless steel autoclave of 50mL teflon lineds, in temperature after sealing
12h, product natural cooling to be synthesized are reacted under conditions of being 200 DEG C；
Product using cylindrical membrane separator-filter is detached, is dried in vacuo at -50 DEG C, obtains iron ion doping carbon amounts
Son point powder.
Obtained iron ion doping carbon quantum dot powder toluene is disperseed again, measuring fluorescence quantum yield is
97.8%.
Embodiment 2
0.134g sodium oxalates, 0.2404g urea, 0.3233g iron chloride and the mixing of 20mL toluene are taken, it is molten to form presoma
Liquid；
Obtained precursor solution is placed in the stainless steel autoclave of 50mL teflon lineds, in temperature after sealing
12h, product natural cooling to be synthesized are reacted under conditions of being 200 DEG C；
Product using cylindrical membrane separator-filter is detached, is dried in vacuo at -50 DEG C, obtains iron ion doping carbon amounts
Son point powder.
Obtained iron ion doping carbon quantum dot powder toluene is disperseed again, measuring fluorescence quantum yield is
97.2%.
Embodiment 3
0.5882g citric acids, 0.1202g urea, 0.1618g iron chloride and the mixing of 20mL toluene are taken, it is molten to form presoma
Liquid；
Obtained precursor solution is placed in the stainless steel autoclave of 50mL teflon lineds, in temperature after sealing
14h, product natural cooling to be synthesized are reacted under conditions of being 180 DEG C；
Product using cylindrical membrane separator-filter is detached, is dried in vacuo at -50 DEG C, obtains iron ion doping carbon amounts
Son point powder.
Obtained iron ion doping carbon quantum dot powder toluene is disperseed again, measuring fluorescence quantum yield is
95.5%.
Embodiment 4
0.2701g oxalic acid, 0.3606g ethylenediamines, 0.5999g ferric sulfate and the mixing of 20mL toluene are taken, it is molten to form presoma
Liquid；
Obtained precursor solution is placed in the stainless steel autoclave of 50mL teflon lineds, in temperature after sealing
10h, product natural cooling to be synthesized are reacted under conditions of being 220 DEG C；
Product using cylindrical membrane separator-filter is detached, is dried in vacuo at 50 DEG C, obtains iron ion doping carbon amounts
Son point powder.
Obtained iron ion doping carbon quantum dot powder toluene is disperseed again, it is 94% to measure fluorescence quantum yield.
Embodiment 5
1.1764g sodium citrates, 0.4808g urea, 0.9678g ferric nitrates and the mixing of 20mL toluene are taken, forms presoma
Solution；
Obtained precursor solution is placed in the stainless steel autoclave of 50mL teflon lineds, in temperature after sealing
16h, product natural cooling to be synthesized are reacted under conditions of being 300 DEG C；
Product using cylindrical membrane separator-filter is detached, is dried in vacuo at -50 DEG C, obtains iron ion doping carbon amounts
Son point powder.
Obtained iron ion doping carbon quantum dot powder toluene is disperseed again, measuring fluorescence quantum yield is
96.6%.
Comparative example
Comparative example 1
The process in embodiment 1 is repeated, difference lies in：Source of iron is not added in, i.e., without iron ion doping.
Obtained non-iron-doped iron doping carbon quantum dot powder toluene is disperseed again, measuring fluorescence quantum yield is
23%.
Comparative example 2
The process in embodiment 1 is repeated, difference lies in：Toluene is replaced as solvent using water.
Obtained iron-doped iron doping carbon quantum dot powder water is disperseed into (since it does not dissolve in organic solvent) again, is surveyed
It is 34% to obtain fluorescence quantum yield.
Experimental example
1 transmission electron microscope of experimental example detects
Transmission electron microscope detection is carried out to the iron ion doping carbon quantum dot that embodiment 1 obtains, structure is as shown in Figure 1.
As seen from Figure 1, there is smaller grain size by the iron ion doping carbon quantum dot that the method for the invention obtains,
Specifically, average grain diameter is 2~10nm.
2 fluorescence property of experimental example detects
(1) fluorescence property detection is carried out to the iron ion doping carbon quantum dot that embodiment 1 obtains, obtains its Three-Dimensional Fluorescence Spectra
Figure and corresponding colored spectrogram, respectively as shown in Figure 2 a and 2 b.As shown in Fig. 2 a and Fig. 2 b, it can be seen that iron ion doping carbon
The a length of 440nm of optimum excitation wave of quantum dot, best launch wavelength are 565nm (yellow lights)；
The iron ion doping carbon quantum that two parts of embodiments 1 obtain is taken respectively to be dissolved in toluene, respectively natural light (left side)
It is irradiated under the ultraviolet light (right side) of 365nm wavelength, as a result as shown in Figure 2 c, obtained iron ion carbon quantum is understood by Fig. 2 c
Point is the transparency liquid (left side) of glassy yellow under natural light, and it is (right that orange-yellow fluorescence is sent out under the ultraviolet light of 365nm wavelength
Side), this is consistent with the result of Fig. 2 a~2b.
(2) fluorescence property detection is carried out to the iron carbon quantum dot of not mixing that comparative example 1 obtains, obtain its three-dimensional fluorogram and
Corresponding colour spectrogram, respectively as shown in Figure 3a and Figure 3b shows.As shown in Fig. 3 a and Fig. 3 b, it can be seen that do not mix iron carbon quantum dot
Launch wavelength depends on the length of excitation wave, has excitation wavelength dependence；
The iron carbon quantum of not mixing that two parts of comparative examples 1 obtain is taken respectively to be dissolved in toluene, respectively natural light (left side) and
It is irradiated under the ultraviolet light (right side) of 365nm wavelength, as a result as shown in Figure 3c, obtained iron ion carbon quantum dot is understood by Fig. 3 c
It is flaxen transparency liquid (left side) under natural light, and is sent out under the ultraviolet light of 365nm wavelength very weak light blue
Fluorescence (right side).
(3) the iron ion doping carbon quantum dot obtained to comparative example 2 (hydro-thermal method) carries out fluorescence property detection, obtain thirdly
Fluorogram and corresponding colored spectrogram are tieed up, respectively as shown in figures 4 a and 4b.As shown in Fig. 4 a and Fig. 4 b, it can be seen that it is most
Good launch wavelength is 440nm or so (blue light)；
Take the iron ion doping carbon quantum that two parts of comparative examples 2 obtain (because it does not dissolve in toluene) respectively soluble in water,
It irradiates under the ultraviolet light (right side) of natural light (left side) and 365nm wavelength, as a result as illustrated in fig. 4 c, is understood by Fig. 4 c made respectively
The iron ion carbon quantum dot obtained is bronzing liquid (left side) under natural light, and sends out day under the ultraviolet light of 365nm wavelength
Blue-fluorescence (right side).
3 XPS of experimental example is detected
The iron ion doping carbon quantum dot obtained to embodiment 1 carries out XPS detections, and the results are shown in Figure 5,
Have 5 peaks at 284.85eV, 400.24eV, 532.35eV, 720.46eV and 1071.84eV, corresponded to respectively C1s, N1s,
The combination energy of O1s, Fe2p and Na1s, this explanation using the method for the invention prepare iron ion doping carbon quantum dot contain C,
N, five kinds of elements of O, Fe and Na, corresponding content is respectively 79%, 2.06%, 5.81%, 18.44%0.24% and 0.26%.
4 fluorescence quantum yield of experimental example detects
Fluorescence quantum yield detection, the fluorescence quantum yield are carried out to the doping iron ion carbon quantum dot that embodiment 1 obtains
For the absolute fluorescence quantum yield measured by integrating sphere, result as shown in Figure 6 a, wherein, the curve of reference represents solvent
Peak, i.e. background peaks.Wherein, obtaining the fluorescence quantum yield (QY) of doping iron ion carbon quantum dot that embodiment 1 obtains is
97.8%.
Equally, to embodiment 2~5 carry out fluorescence quantum yield detection, respectively 97.2%, 95.5%, 94% and
96.6%.
Also, the detection of fluorescence quantum yield is carried out to the product that comparative example 1~2 obtains, as shown in figures 6 a and 6b,
Fluorescence quantum yield is respectively 23% and 34%.
5 Water in Organic Solvents content detection of experimental example
The water content that the iron ion doping carbon quantum dot obtained using embodiment 1 is carried out in organic solvent is examined
It surveys：
(1) fluorescence property in the acetonitrile solution for being 10% in water content to the iron ion doping carbon quantum dot is examined
It surveys, the results are shown in Figure 7, and showing 565nm at the intensity (440nm excitations) of fluorescence of transmitting, change with time figure, can see
Go out, fluorescence intensity just no longer changed after 1 minute, therefore can be set to detection time 1 minute, realized for organic solvent
The quick detection of middle water content.
(2) to the iron ion doping carbon quantum dot in the acetonitrile solution of different water contents (0~10%) after 1 minute
Fluorescence property is detected, the results are shown in Figure 8 (wherein, from top to bottom, water content (V/V, %) be followed successively by 0,0.001,
0.01st, 0.1,0.3,0.5,0.8,1,1.5,2,4,6,8,10, Fig. 8 shows that the iron ion doping carbon quantum dot contains in different water
Fluorescent emission spectrogram (excitation wavelength 440nm) in the acetonitrile solution of amount after 1 minute, as shown in Figure 8, with the increasing of water content
Add, the fluorescence of iron ion doping carbon quantum dot is gradually quenched.
Wherein, fluorescent quenching and the correspondence of different water contents in Fig. 8, can arrange as shown in Fig. 9.
(3) linear expression is carried out to the result (shown in Fig. 8 and 9) that above-mentioned (2) obtain, the results are shown in Figure 10, it is known that,
For water content between 0%-2%, fluorescent quenching value presents good linear relationship with water content, wherein, R2It is 0.9943,
Detection limit can realize the detection of analysis level up to 0.01%.
The present invention is described in detail above in association with preferred embodiment and exemplary example.But need what is stated
It is that these specific embodiments are only the illustrative explanations to the present invention, do not form any limit to protection scope of the present invention
System.In the case of without departing from spirit and scope of the present invention, the technology of the present invention content and embodiments thereof can be carried out
Various improvement, equivalencing or modification, these are each fallen in protection scope of the present invention.Protection scope of the present invention is with appended power
Subject to profit requirement.
Claims (10)
1. a kind of preparation method of iron ion doping carbon quantum dot, which is characterized in that the described method comprises the following steps：
Step 1 adds in carbon source, nitrogen source and source of iron in organic solvent, forms precursor solution；
Precursor solution described in step 1 is placed in reaction kettle by step 2, is reacted, preferably cooled down after reaction；
Step 3 is post-processed, and obtains iron ion doping carbon quantum dot.
2. preparation method according to claim 1, which is characterized in that in step 1, the carbon source is selected from carbon elements
Organic matter；Preferably, the carbon source is selected from the organic matter containing-COOH and/or-COONa, such as the organic matter containing-COONa；
It is highly preferred that the carbon source is selected from one or more of sodium citrate, citric acid, oxalic acid and sodium oxalate, such as sodium citrate.
3. preparation method according to claim 1 or 2, which is characterized in that in step 1, the nitrogen source is selected from nitrogenous member
The organic matter of element, is preferably selected from ethylenediamine and/or urea, such as urea.
4. the preparation method according to one of claims 1 to 3, which is characterized in that in step 1, the source of iron is selected from iron
Ion salt is preferably selected from one or more of iron chloride, ferric sulfate, ferric nitrate and ferric acetate, such as iron chloride.
5. the preparation method according to one of Claims 1-4, which is characterized in that in step 1, the organic solvent choosing
From one or more of benzene,toluene,xylene, ethyl alcohol, tetrahydrofuran and carbon tetrachloride, it is preferably selected from benzene, toluene and diformazan
One or more of benzene, such as toluene.
6. the preparation method according to one of claim 1 to 5, which is characterized in that in the precursor solution,
The molar concentration of the carbon source be 0.01-10mol/L, more preferably preferably 0.01-1mol/L, 0.05-0.5mol/L,
Such as 0.05~0.2mol/L；And/or
The molar concentration of the nitrogen source be 0.01-10mol/L, more preferably preferably 0.02-2mol/L, 0.05-0.5mol/L,
Such as 0.1~0.3mol/L；And/or
The molar concentration of the source of iron is 0.05-10mol/L, more preferably preferably 0.05-0.5mol/L, 0.05-0.2mol/
L, such as 0.1mol/L；
Wherein, the molar concentration of source of iron is with the molar concentration meter of wherein ferro element.
7. the preparation method according to one of claim 1 to 6, which is characterized in that
In step 2, the reaction is following carries out：At 100~500 DEG C carry out 5~50h, be preferable at 150~300 DEG C into
Row 8~for 24 hours, 10~14h, such as 200 DEG C of reaction 12h are carried out more preferably at 180~220 DEG C；And/or
In step 3, the post processing includes separation and drying, it is preferable that the separation is using cylindrical membrane separator-filter
Or centrifugal process is detached, it is highly preferred that the drying is vacuum freeze drying or vacuum and heating drying, such as vacuum refrigeration
It is dry.
8. a kind of iron ion doping carbon quantum dot, it is preferred to use it is prepared by one of claim 1 to 7 the method, wherein,
The average grain diameter of the iron ion doping carbon quantum dot is 2~10nm, preferably 2~8nm；And/or
The fluorescence quantum yield of the iron ion doping carbon quantum dot is more than 90%, such as 97.8%；And/or
The iron ion doping carbon quantum dot sends out orange-yellow fluorescence under ultraviolet excitation.
9. according to iron described in the iron ion doping carbon quantum dot or claim 8 that one of claim 1 to 7 the method obtains from
The application of son doping carbon quantum dot, as fluorescence probe, analysis detection is carried out to the water content in organic solvent.
10. application according to claim 9, wherein, the iron ion doping carbon quantum dot is to Water in Organic Solvents content
Detection limit up to 0.01%.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109060753A (en) * | 2018-09-12 | 2018-12-21 | 天津科技大学 | A kind of low cost visualization quickly detects the new method of Water in Organic Solvents part content |
| CN109679651A (en) * | 2019-01-24 | 2019-04-26 | 安徽师范大学 | Fe2O3 doping carbon dots and its preparation method and application with Mimetic Peroxidase property |
| CN110669518A (en) * | 2019-11-21 | 2020-01-10 | 中国林业科学研究院林产化学工业研究所 | Fluorescent carbon dot and preparation method and application thereof |
| CN111196923A (en) * | 2020-01-17 | 2020-05-26 | 合肥工业大学 | Acidic mine wastewater modified carbon quantum dot and preparation method and application thereof |
| CN112408362A (en) * | 2019-08-21 | 2021-02-26 | 中国石油大学(北京) | Carbon quantum dot and preparation method and application thereof |
| CN112608743A (en) * | 2020-12-24 | 2021-04-06 | 中国矿业大学(北京) | Preparation method of coal-based fluorescent carbon quantum dots |
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| CN116376362A (en) * | 2023-06-06 | 2023-07-04 | 江苏唐彩新材料科技股份有限公司 | Water-based ink and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032462A (en) * | 2015-07-03 | 2015-11-11 | 沈阳大学 | Preparation method of iron and nitrogen doped carbon nanoparticle photocatalyst |
| CN105838363A (en) * | 2016-04-21 | 2016-08-10 | 大连理工大学 | Method for synthesizing carbon quantum dots on basis of amino acids and iron ions |
| WO2017030907A1 (en) * | 2015-08-14 | 2017-02-23 | Imerys Usa, Inc. | Compositions and methods for providing fluorescing materials |
| CN106783187A (en) * | 2016-12-27 | 2017-05-31 | 常州大学 | A kind of preparation method of island shape in-situ carbon coated iron oxide light anode composite membrane |
-
2018
- 2018-01-19 CN CN201810065962.3A patent/CN108251108B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032462A (en) * | 2015-07-03 | 2015-11-11 | 沈阳大学 | Preparation method of iron and nitrogen doped carbon nanoparticle photocatalyst |
| WO2017030907A1 (en) * | 2015-08-14 | 2017-02-23 | Imerys Usa, Inc. | Compositions and methods for providing fluorescing materials |
| CN105838363A (en) * | 2016-04-21 | 2016-08-10 | 大连理工大学 | Method for synthesizing carbon quantum dots on basis of amino acids and iron ions |
| CN106783187A (en) * | 2016-12-27 | 2017-05-31 | 常州大学 | A kind of preparation method of island shape in-situ carbon coated iron oxide light anode composite membrane |
Non-Patent Citations (2)
| Title |
|---|
| WEIQIANG YANG等: "High peroxidase-like activity of iron and nitrogen co-doped carbon dots and its application in immunosorbent assay", 《TALANTA》 * |
| 李洪仁等: "一步合成铁氮掺杂碳纳米粒子及其可见光催化", 《无机化学学报》 * |
Cited By (15)
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|---|---|---|---|---|
| CN109060753A (en) * | 2018-09-12 | 2018-12-21 | 天津科技大学 | A kind of low cost visualization quickly detects the new method of Water in Organic Solvents part content |
| CN109679651B (en) * | 2019-01-24 | 2022-04-12 | 安徽师范大学 | Iron-doped carbon dots with peroxide mimic enzyme property and preparation method and application thereof |
| CN109679651A (en) * | 2019-01-24 | 2019-04-26 | 安徽师范大学 | Fe2O3 doping carbon dots and its preparation method and application with Mimetic Peroxidase property |
| CN112408362A (en) * | 2019-08-21 | 2021-02-26 | 中国石油大学(北京) | Carbon quantum dot and preparation method and application thereof |
| CN110669518A (en) * | 2019-11-21 | 2020-01-10 | 中国林业科学研究院林产化学工业研究所 | Fluorescent carbon dot and preparation method and application thereof |
| CN111196923A (en) * | 2020-01-17 | 2020-05-26 | 合肥工业大学 | Acidic mine wastewater modified carbon quantum dot and preparation method and application thereof |
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| CN113813981A (en) * | 2021-09-30 | 2021-12-21 | 中国科学院城市环境研究所 | Synthesis of space separated metal nitride quantum dot catalyst and its environment application |
| CN113813981B (en) * | 2021-09-30 | 2024-02-13 | 中国科学院城市环境研究所 | Synthesis of space-division type metal nitride quantum dot catalyst and environmental application thereof |
| CN114392657A (en) * | 2022-03-25 | 2022-04-26 | 中国科学院宁波材料技术与工程研究所 | Asymmetric multifunctional heterogeneous composite membrane and preparation method and application thereof |
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