CN108251107A - A kind of preparation of ZnO thin film carbon quantum dot and obtained carbon quantum dot and application - Google Patents
A kind of preparation of ZnO thin film carbon quantum dot and obtained carbon quantum dot and application Download PDFInfo
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- CN108251107A CN108251107A CN201810054717.2A CN201810054717A CN108251107A CN 108251107 A CN108251107 A CN 108251107A CN 201810054717 A CN201810054717 A CN 201810054717A CN 108251107 A CN108251107 A CN 108251107A
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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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- 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
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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 ZnO thin film carbon quantum dot, wherein, carbon source, nitrogen source and cobalt source are scattered in organic solvent, solvent thermal reaction is carried out, obtains the ZnO thin film 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 ZnO thin film carbon quantum dot has very high fluorescence quantum yield, reaches as high as 93%；Meanwhile fluorescence property is good in organic solvent for ZnO thin film 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 ZnO thin film 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 cobalt source in organic solvent
Middle reaction, obtains a kind of ZnO thin film carbon quantum dot, and there is the ZnO thin film carbon quantum size uniformity, fluorescent quantum to produce
The advantages of rate height (reaching as high as 93%), also, fluorescence property is good in organic solvent for the ZnO thin film carbon quantum dot,
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, so as to complete
Into the present invention.
One of the objects of the present invention is to provide a kind of preparations of ZnO thin film carbon quantum dot, are embodied in following several
A aspect：
(1) a kind of preparation method of ZnO thin film carbon quantum dot, wherein, it the described method comprises the following steps：
Step 1 adds in carbon source, nitrogen source and cobalt source 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 ZnO thin film 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 cobalt source be selected from cobalt from
Alite class is preferably selected from one or more of cobalt chloride, cobaltous sulfate, cobalt nitrate and cobalt acetate, such as cobalt 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 cobalt source is 0.05-10mol/L, more preferably preferably 0.05-0.5mol/L, 0.05-
0.2mol/L, such as 0.1mol/L.
(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 ZnO thin film carbon quantum dot, is embodied in following side
Face：
(8) a kind of ZnO thin film 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 ZnO thin film carbon quantum dot is 2~10nm, preferably 2~8nm；And/or
The fluorescence quantum yield of the ZnO thin film carbon quantum dot is more than 85%, preferably more than 90%；And/or
The ZnO thin film 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 ZnO thin film carbon quantum dot, be embodied in
Under several aspects：
(9) described in the ZnO thin film 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 ZnO thin film carbon quantum dot.
(10) application according to above-mentioned (9), wherein, the ZnO thin film 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 ZnO thin film carbon quantum dot prepared by embodiment 1；
The three-dimensional fluorescence spectrogram and correspondence of the ZnO thin film 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 ZnO thin film 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 not mixing cobalt ions 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 prepared by comparative example 1 does not mix cobalt ions carbon quantum dot on natural light (left side) and 365nm the wavelength (right side
Side) ultraviolet light under fluorescent emission picture；
The three-dimensional fluorescence spectrogram and correspondence of the ZnO thin film 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 ZnO thin film 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 ZnO thin film 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 is shown in the dioxane solution that ZnO thin film carbon quantum dot prepared by embodiment 1 is 10% in water content
Change with time the intensity (440nm excitations) of the fluorescence emitted at 565nm figure；
Fig. 8 shows fluorescence of the ZnO thin film carbon quantum dot of the preparation of embodiment 1 in the dioxane of different moisture content
Spectrogram；
Fig. 9 shows two-dimentional correspondence figure of the fluorescent quenching from different water contents；
Figure 10 shows that the standard of water content in ZnO thin film carbon quantum dot detection dioxane prepared by embodiment 1 is bent
Line.
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 ZnO thin film carbon quantum dot, and the method includes following steps
Suddenly：
Step 1 adds in carbon source, nitrogen source and cobalt source 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 cobalt source is selected from cobalt ions salt.
In further preferred embodiment, in step 1, the cobalt source be selected from cobalt chloride, cobaltous sulfate, cobalt nitrate and
One or more of cobalt acetate, such as cobalt chloride.
Wherein, inventor has found that the carbon quantum dot that preparation is doped using cobalt ions can be apparent by many experiments
Improve the fluorescence quantum yield of carbon quantum dot.Wherein, the fluorescence quantum yield of ZnO thin film carbon quantum dot of the present invention can
To reach 93%.Also, obtained ZnO thin film carbon quantum dot can steadily emit yellow light, and carbon quantum of the prior art
Point generally all emits blue light, and still, blue light is not eye-catching, and especially when being applied on biology, in cell imaging, cell tissue is in itself
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 93%；(2) compared to hydro-thermal method, the cobalt ions that the method for the invention obtains is more suitable for answering commercial Application, profit
In for industries such as weavings, 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 cobalt source
For 0.05-10mol/L.
In further preferred embodiment, in the precursor solution, the molar concentration of the cobalt source is 0.05-
0.5mol/L。
In embodiment still more preferably, in the precursor solution, the molar concentration of the cobalt source is
0.05-0.2mol/L, such as 0.1mol/L.
Wherein, the molar concentration of the cobalt source is with the molar concentration meter of wherein cobalt ions.Inventor passes through many experiments
It was found that with the increase of Co doping amounts, fluorescence property enhancing still, continues the increase with Co doping amounts, fluorescence property is not
It can further enhance, 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 ZnO thin film 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 ZnO thin film 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 ZnO thin film carbon quantum dot for 2~
10nm。
In further preferred embodiment, the average grain diameter of the ZnO thin film carbon quantum dot is 2~8nm.
According to a kind of preferred embodiment of the present invention, the fluorescence quantum yield of the ZnO thin film carbon quantum dot is
More than 85%.
In further preferred embodiment, the fluorescence quantum yield of the ZnO thin film carbon quantum dot for 90% with
On, such as 93%.
Wherein, it is produced using the ZnO thin film carbon quantum dot that the method for the invention obtains with very high fluorescent quantum
Rate reaches more than 85%, especially more than 90%, reaches as high as 93%.But in the prior art, the carbon quantum dot
Fluorescence quantum yield is generally 10% or so, increases even by the fluorescence quantum yield after other element dopings,
It is only capable of reaching 30%.
According to a kind of preferred embodiment of the present invention, the ZnO thin film carbon quantum dot is sent out under ultraviolet excitation
Orange-yellow fluorescence.
Wherein, ZnO thin film 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 ZnO thin film carbon quantum dot and differs markedly from carbon quantum dot described in the prior art.
Third aspect present invention provides ZnO thin film made from a kind of preparation method described according to a first aspect of the present invention
The application of ZnO thin film 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 ZnO thin film 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 ZnO thin film 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 ZnO thin film carbon quantum dot to Water in Organic Solvents content
Limit is surveyed up to 0.01%.
Wherein, ZnO thin film 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) ZnO thin film carbon quantum dot of the present invention has smaller grain size, and average grain diameter is 2~10nm；
(4) ZnO thin film carbon quantum dot of the present invention has very high fluorescence quantum yield, reaches more than 85%,
Especially more than 90%, such as 93%, this is significantly unlike the prior art；
(5) ZnO thin film carbon quantum dot of the present invention sends out orange-yellow fluorescence under ultraviolet light；
(6) ZnO thin film 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, 0.2588g cobalt chlorides 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 ZnO thin film carbon amounts
Son point powder.
Obtained ZnO thin film carbon quantum dot powder toluene is disperseed again, measuring fluorescence quantum yield is
91.0%.
Embodiment 2
0.134g sodium oxalates, 0.2404g urea, 0.2588g cobalt chlorides 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 ZnO thin film carbon amounts
Son point powder.
Obtained ZnO thin film carbon quantum dot powder toluene is disperseed again, it is 93% to measure fluorescence quantum yield.
Embodiment 3
0.5882g citric acids, 0.1202g urea, 0.1295g cobalt chlorides 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 ZnO thin film carbon amounts
Son point powder.
Obtained ZnO thin film carbon quantum dot powder toluene is disperseed again, measuring fluorescence quantum yield is
88.5%.
Embodiment 4
0.2701g oxalic acid, 0.3606g ethylenediamines, 0.8732g cabaltous nitrate hexahydrates and the mixing of 20mL toluene are taken, before formation
Drive liquid solution；
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 ZnO thin film carbon amounts
Son point powder.
Obtained ZnO thin film carbon quantum dot powder toluene is disperseed again, measuring fluorescence quantum yield is
89.8%.
Embodiment 5
1.1764g sodium citrates, 0.4808g urea, 0.7083g cobalt acetates 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 ZnO thin film carbon amounts
Son point powder.
Obtained ZnO thin film carbon quantum dot powder toluene is disperseed again, measuring fluorescence quantum yield is
90.6%.
Comparative example
Comparative example 1
The process in embodiment 1 is repeated, difference lies in：Cobalt source is not added in, i.e., without ZnO thin film.
Obtained ZnO thin film carbon quantum dot powder toluene of not mixing 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 ZnO thin film carbon quantum dot powder water of mixing is disperseed into (since it does not dissolve in organic solvent) again, is surveyed
It is 30% to obtain fluorescence quantum yield.
Experimental example
1 transmission electron microscope of experimental example detects
Transmission electron microscope detection is carried out to the ZnO thin film 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 ZnO thin film 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 ZnO thin film 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 ZnO thin film carbon
The a length of 440nm of optimum excitation wave of quantum dot, best launch wavelength are 565nm (yellow lights)；
The ZnO thin film 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 cobalt ions 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 cobalt 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 cobalt carbon quantum dot
Launch wavelength depends on the length of excitation wave, has excitation wavelength dependence；
The cobalt 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 cobalt ions 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 ZnO thin film 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 (faint blue light)；
Take the ZnO thin film 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 cobalt ions carbon quantum dot obtained is bronzing liquid (left side) under natural light, and sends out indigo plant under the ultraviolet light of 365nm wavelength
Color fluorescence (right side).
Experimental example 3XPS is detected
XPS detections are carried out to the ZnO thin film carbon quantum dot that embodiment 1 obtains, the results are shown in Figure 5,
There are 4 peaks at 284.76eV, 400.22eV, 532.24eV, 785.98eV, corresponded to the combination of C1s, N1s, O1s, Co2p respectively
Can, this explanation contains tetra- kinds of elements of C, N, O and Co using ZnO thin film carbon quantum dot prepared by the method for the invention, corresponding
Content be respectively 77.45%, 4.55%, 17.73%, 0.26%.
4 fluorescence quantum yield of experimental example detects
Fluorescence quantum yield detection, the fluorescence quantum yield are carried out to the doping cobalt ions 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 cobalt ions carbon quantum dot that embodiment 1 obtains is
91.0%.
Equally, to embodiment 2~5 carry out fluorescence quantum yield detection, respectively 93%, 88.5%, 89.8% and
90.6%.
Also, the detection of fluorescence quantum yield is carried out to the product that comparative example 1~2 obtains, respectively such as Fig. 6 b and Fig. 6 c institutes
Show, fluorescence quantum yield is respectively 23% and 27%.
5 Water in Organic Solvents content detection of experimental example
The water content that the ZnO thin film carbon quantum dot obtained using embodiment 1 is carried out in organic solvent is examined
It surveys：
(1) to the ZnO thin film carbon quantum dot water content be 10% dioxane solution in fluorescence property into
Row detection, the results are shown in Figure 7, and showing 565nm at the intensity (440nm excitations) of fluorescence of transmitting, change with time figure, can
To find out, fluorescence intensity just no longer changed after 1 minute, therefore can be set to detection time 1 minute, realized for organic
The quick detection of water content in solvent.(2) to dioxy of the ZnO thin film carbon quantum dot in different water contents (0~10%)
Fluorescence property in six ring solution after 1 minute is detected, the results are shown in Figure 8 (wherein, from top to bottom, water content (V/
V, %) be followed successively by 0,0.01,0.4,0.8,2,4,6,8,10, Fig. 8 show that the ZnO thin film carbon quantum dot contains in different water
Fluorescent emission spectrogram (excitation wavelength 440nm) in the dioxane solution of amount after 1 minute, as shown in Figure 8, with water content
Increase, the fluorescence of ZnO thin film 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 0.9963,
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 ZnO thin film carbon quantum dot, which is characterized in that the described method comprises the following steps：
Step 1 adds in carbon source, nitrogen source and cobalt source 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 ZnO thin film 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 cobalt source is selected from cobalt
Ion salt is preferably selected from one or more of cobalt chloride, cobaltous sulfate, cobalt nitrate and cobalt acetate, such as cobalt 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 cobalt source is 0.05-10mol/L, more preferably preferably 0.05-0.5mol/L, 0.05-0.2mol/
L, such as 0.1mol/L.
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 ZnO thin film 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 ZnO thin film carbon quantum dot is 2~10nm, preferably 2~8nm；And/or
The fluorescence quantum yield of the ZnO thin film carbon quantum dot is more than 85%, preferably more than 90%；And/or
The ZnO thin film carbon quantum dot sends out orange-yellow fluorescence under ultraviolet excitation.
9. according to cobalt described in the ZnO thin film 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 ZnO thin film carbon quantum dot is to Water in Organic Solvents content
Detection limit up to 0.01%.
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