CN104774612A - Preparation method of dual-wavelength fluorescence/dual-wavelength electrochemiluminescence carbon quantum dots - Google Patents
Preparation method of dual-wavelength fluorescence/dual-wavelength electrochemiluminescence carbon quantum dots Download PDFInfo
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Abstract
The invention relates to a preparation method of dual-wavelength fluorescence/dual-wavelength electrochemiluminescence carbon quantum dots, belonging to the technical field of novel carbon nano materials and preparation thereof. The method comprises the following steps: mixing activated carbon and a strong alkali, carrying out ball milling, and carrying out ultrafiltration separation to obtain an orange carbon quantum dot solution. The quantum dots have the properties of dual-wavelength fluorescence and dual-wavelength electrochemiluminescence. The synthesis method is simple and effective, has the advantages of cheap and accessible raw materials, mild reaction conditions and environment friendliness, and can easily implement large-scale production of carbon quantum dots. Besides, the carbon quantum dots prepared by the method contain abundant oxygen-containing functional groups, have favorable water solubility, and have the properties of dual-wavelength fluorescence and dual-wavelength electrochemiluminescence.
Description
Technical field
The invention belongs to carbon nanomaterial and preparing technical field thereof, particularly relate to a kind of preparation method with the carbon quantum dot of double wave length fluorescent and dual wavelength electrogenerated chemiluminescence(ECL) character.
Background technology
Carbon quantum dot is that a kind of particle diameter is less than 10nm, has the torispherical nano particle of good dispersion.There is due to it advantages such as good water-soluble, high fluorescent stability, low preparation cost, hypotoxicity and good biocompatibility, cause the extensive concern of people.Especially the fluorescence of carbon quantum dot uniqueness and the character of electrogenerated chemiluminescence(ECL), makes it have broad prospect of application in the field such as bio-sensing and bio-imaging.
Current preparation has the method for fluorescence and electrogenerated chemiluminescence(ECL) character carbon quantum dot based on microwave method, electrochemical oxidation process and chemical oxidization method.At document (1) Adv.Funct.Mater., 2012,22, in 2971-2979, the people such as L.L.Li are under nitration mixture condition, utilize microwave heating graphene oxide nanometer sheet solution, obtain the carbon quantum dot with yellow-green colour (before reduction) and blueness (after reduction) fluorescence, and the carbon quantum dot with yellow-green fluorescence also has electrogenerated chemiluminescence(ECL) character.At document (2) J.Am.Chem.Soc., in 2009,131,4564-4565, the people such as L.Y.Zheng utilize the method for electrolytic graphite rod to prepare the carbon quantum dot with fluorescence and electrogenerated chemiluminescence(ECL) character.At document (3) Carbon, 2013,56, in 12-17, gac and nitration acid heat reflux by the people such as Y.Q.Dong, then through ultra-filtration and separation, obtain the carbon quantum dot with yellow fluorescence, and this carbon quantum dot and sulphite form electrogenerated chemiluminescence(ECL) system.
But adopt the method such as microwave method, electrochemical oxidation process and chemical oxidization method to prepare carbon quantum dot and there is certain limitation, as high in raw materials cost, carbon quantum dot quantum yield is low, last handling process is complicated, is therefore all difficult to scale production carbon quantum dot.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of double wave length fluorescent and dual wavelength electrogenerated chemiluminescence(ECL) carbon quantum dot.The method is ball milling after being mixed with highly basic by gac, and then obtain orange-yellow carbon quantum dot solution by ultra-filtration and separation, this quantum dot has the character of double wave length fluorescent and dual wavelength electrogenerated chemiluminescence(ECL).Concrete technology step is as follows:
(1) be that the two to mix and this biased sample is put into stainless cylinder of steel by the ratio of 1:1 ~ 1:2 according to gac and the mass ratio of highly basic, the ratio being 1:50 ~ 1:70 according to the mass ratio of biased sample and Stainless Steel Ball takes Stainless Steel Ball and is added by Stainless Steel Ball in stainless cylinder of steel, the cumulative volume of biased sample and Stainless Steel Ball accounts for 1/4 ~ 1/2 of stainless steel tank volume, with the rotating speed ball milling 40 ~ 70 hours of 400 ~ 600 revs/min.Wherein, described highly basic is any one in potassium hydroxide or sodium hydroxide.
(2) after ball milling step (1) obtained, sample dispersion is in deionized water, wherein after ball milling, the mass ratio of sample and deionized water is 1:40 ~ 1:60, ultrasonic disperse 10 ~ 30 minutes, then being neutralized to pH with strong acid solution is 7.0, with the rotating speed of 5000 ~ 9000 revs/min, (this rotating speed is equivalent to the universal gravity constant of 2795 ~ 9055 times, be typically expressed as 2795 ~ 9055 × g) centrifugal 5 ~ 10 minutes, get supernatant liquor in super filter tube, with the centrifugation of high molecular weight cut-off super filter tube, get filtrate with the further centrifugation of low catching molecular super filter tube, and add deionized water wash 5 ~ 8 times, until filtrate is become colorless by yellow, get and retain part for orange-yellow carbon quantum dot solution.Wherein, described strong acid is any one in nitric acid, hydrochloric acid or sulfuric acid, and its concentration is 0.1 ~ 0.3mol L
-1; The molecular weight cut-off of described high molecular weight cut-off super filter tube is 30,50 or 100kDa in one, the molecular weight cut-off of low catching molecular super filter tube be 3 or 10kDa in one, high molecular weight cut-off super filter tube and low catching molecular super filter tube are combined, to obtain the carbon quantum dot of different size.
Adopt Jeol Ltd. JEM-2100F type high resolution transmission electron microscopy (HRTEM) to characterize the pattern of this carbon quantum dot, as shown in Figure 1, product size is more homogeneous, and particle diameter is at about 2.2nm for test result.Adopt German Brooker company Vertex 70V type Fourier transform infrared spectroscopy (FTIR) to characterize this carbon quantum dot, as shown in Figure 2, show that this carbon quantum dot contains abundant hydroxyl and carboxyl functional group.Rigaku company D/MAX2500VB2+/PC type x-ray diffractometer (XRD) is adopted to characterize this carbon quantum dot, as shown in Figure 3, the spacing of lattice of carbon quantum dot is 0.403nm, slightly larger than the spacing of lattice of Graphene, analysis is that carbon quantum dot contains caused by the large interlamellar spacing of abundant surface functional group support.U.S. Perkinelmer Inc. Lambda 35 type ultraviolet-visible pectrophotometer (UV-Vis) is adopted to survey its ultraviolet-visible absorption spectroscopy, as shown in Figure 4, product is without obvious ultraviolet and visible absorption peak, but there is very wide absorption band at below 550nm, illustrate that this carbon quantum dot contains abundant oxygen-containing functional group.Japanese Shimadzu RF-5301PC type spectrophotofluorometer is adopted to survey its fluorescence (PL) spectrum under different excitation wavelength, as shown in Figure 5.This carbon quantum dot, in the excitation wavelength range of 290 ~ 390nm, has two partly overlapping emission peaks under each excitation wavelength.As can be seen from Figure 5, first emission peak does not move along with the change of excitation wavelength, and emission maximum peak position is at 490nm, and second emission peak red shift along with the increase of excitation wavelength.Adopt the Electrochemiluminescprocess process instrument of Rui Mai analytical instrument company to survey its electrogenerated chemiluminescence(ECL) character, then by successively by Single wavelength infiltration type spectral filter (wavelength is respectively 425,440,460,475,490,505,520,535,555,575,590,620,640,665,690,715,740 and 765nm) be positioned over bottom reaction tank, cover and carry out electrochemiluminescdetection detection after photomultiplier and obtain its electrogenerated chemiluminescence(ECL) (ECL) spectrogram, as shown in Figure 6, this carbon quantum dot has dual wavelength electrogenerated chemiluminescence(ECL) character.
Feature of the present invention and advantage are: adopt high-energy ball milling method to prepare carbon quantum dot, synthetic method is simply effective, and cheaper starting materials is easy to get, and the gentle and environmental friendliness of reaction conditions, is easy to scale production carbon quantum dot.In addition, the carbon quantum dot adopting the inventive method to prepare contains abundant oxygen-containing functional group, good water solubility, has double wave length fluorescent and dual wavelength electrogenerated chemiluminescence(ECL) character.
Accompanying drawing explanation
The HRTEM photo of the carbon quantum dot that Fig. 1 provides for the embodiment of the present invention 1.
The carbon quantum dot FTIR spectrogram that Fig. 2 provides for the embodiment of the present invention 1.Wherein, X-coordinate is wave number, and unit is: centimetre
-1(cm
-1), ordinate zou is transmittance, and unit is: percentage ratio (%).
The XRD spectra of the carbon quantum dot that Fig. 3 provides for the embodiment of the present invention 1.Wherein, X-coordinate is angle 2 θ, and unit is: degree (°); Ordinate zou is diffracted intensity, and unit is: absolute units (a.u.).
The UV-Vis spectrogram of the carbon quantum dot that Fig. 4 provides for the embodiment of the present invention 1.Wherein, X-coordinate is wavelength, and unit is: nanometer (nm), ordinate zou is absorbancy, without unit.
The PL spectrogram of the carbon quantum dot that Fig. 5 provides for the embodiment of the present invention 1 (excitation wavelength by 250nm to 530nm, step-length 20nm).Wherein, X-coordinate is wavelength, and unit is: nanometer (nm), and ordinate zou is peak intensity, and unit is: absolute units (a.u.).
The ECL spectrogram of the carbon quantum dot that Fig. 6 provides for the embodiment of the present invention 1.Wherein, X-coordinate is wavelength, and unit is: nanometer (nm), and ordinate zou is peak intensity, and unit is: absolute units (a.u.).
Embodiment
Embodiment 1:
Take 2g gac and 4g potassium hydroxide in stainless cylinder of steel, add the large ball of stainless steel that 9 diameters are 20mm again, 20 diameters are that in the stainless steel of 10mm, ball and 50 diameters are the stainless steel bead (mass ratio of biased sample and Stainless Steel Ball is 1:70) of 6mm, the cumulative volume of biased sample and Stainless Steel Ball accounts for 1/2 of stainless steel tank volume, with the rotating speed ball milling 50h of 500rpm.Getting 0.6g milled sample, add 30mL deionized water, ultrasonic disperse 10min, is 0.2mol L by concentration
-1nitric acid is neutralized to pH=7, and 5000 revs/min of (2795 × g) centrifugal 10min, discard precipitation, obtain orange-yellow supernatant liquid.Supernatant liquid is loaded in the super filter tube of 30kDa, centrifugation, get filtrate.Again filtrate is loaded in the super filter tube of 3kDa, centrifugation, then add washed with de-ionized water and become colorless by yellow to filtrate for 6 times, get and retain part, namely obtain orange-yellow carbon quantum dot solution.
Fig. 1 is the HRTEM photo of above-mentioned carbon quantum dot, and as can be seen from the figure, product size is more homogeneous, and particle diameter is at about 2.2nm.Fig. 2 is the FTIR spectrogram of above-mentioned carbon quantum dot, and as can be seen from the figure, this carbon quantum dot contains abundant hydroxyl and carboxyl functional group.Fig. 3 is the XRD spectra of above-mentioned carbon quantum dot, and as can be seen from the figure, the spacing of lattice of this carbon quantum dot is 0.403nm, slightly larger than the spacing of lattice of Graphene, and analysis is because carbon quantum dot contains abundant surface functional group, has supportted large caused by interlamellar spacing.Fig. 4 is the UV-Vis spectrogram of above-mentioned carbon quantum dot, and as can be seen from the figure, this carbon quantum dot without obvious ultraviolet and visible absorption peak, but has very wide absorption band at below 550nm, illustrates that this carbon quantum dot contains abundant oxygen-containing functional group.Fig. 5 is the PL spectrogram of above-mentioned carbon quantum dot, and as can be seen from the figure, this carbon quantum dot, in 290 excitation wavelength range to 390nm, has two partly overlapping emission peaks under each excitation wavelength.Further, first emission peak does not move along with the change of excitation wavelength, and emission maximum peak position is at 490nm, and second emission peak red shift along with the increase of excitation wavelength.Fig. 6 is the ECL spectrogram of above-mentioned carbon quantum dot, and as can be seen from the figure, this carbon quantum dot has the character of dual wavelength electrogenerated chemiluminescence(ECL).
Embodiment 2:
Take 2g gac and 2g potassium hydroxide in stainless cylinder of steel, add the large ball of stainless steel that 7 diameters are 20mm again, 10 diameters are that in the stainless steel of 10mm, ball and 50 diameters are the stainless steel bead (mass ratio of biased sample and Stainless Steel Ball is 1:60) of 6mm, the cumulative volume of biased sample and Stainless Steel Ball accounts for 1/3 of stainless steel tank volume, with the rotating speed ball milling 40h of 600rpm.Getting 0.6g milled sample, add 24mL deionized water, ultrasonic disperse 20min, is 0.1mol L by concentration
-1sulfuric acid is neutralized to pH=7, and 9000 revs/min of (9055 × g) centrifugal 5min, discard precipitation, obtain orange-yellow supernatant liquid.Supernatant liquid is loaded in the super filter tube of 100kDa, centrifugation, get filtrate.Again filtrate is loaded in the super filter tube of 10kDa, centrifugation, then add washed with de-ionized water 8 times, until filtrate is become colorless by yellow, get and retain part, namely obtain orange-yellow carbon quantum dot solution.
Embodiment 3:
Take 2g gac and 4g sodium hydroxide in stainless cylinder of steel, add the large ball of stainless steel that 7 diameters are 20mm again, 10 diameters are that in the stainless steel of 10mm, ball and 30 diameters are the stainless steel bead (mass ratio of biased sample and Stainless Steel Ball is 1:50) of 6mm, the cumulative volume of biased sample and Stainless Steel Ball accounts for 1/4 of stainless steel tank volume, with the rotating speed ball milling 70h of 400rpm.Getting 0.6g milled sample, add 36mL deionized water, ultrasonic disperse 30min, is 0.3mol L by concentration
-1hydrochloric acid is neutralized to pH=7, and 7000 revs/min of (5478 × g) centrifugal 7min, discard precipitation, obtain orange-yellow supernatant liquid.Supernatant liquid is loaded in the super filter tube of 50kDa, centrifugation, get filtrate.Again filtrate is loaded in the super filter tube of 3kDa, centrifugation, then add washed with de-ionized water 5 times, until filtrate is become colorless by yellow, get and retain part, namely obtain orange-yellow carbon quantum dot solution.
Above-mentioned example is citing of the present invention, although in order to illustration purpose discloses most preferred embodiment of the present invention and accompanying drawing, but not for limiting the present invention, any those of ordinary skill in the art, without departing from the spirit and scope of the invention and the appended claims, various replacement, change and amendment are all possible.Therefore, the present invention should not be limited to the content disclosed in most preferred embodiment and accompanying drawing.
Claims (4)
1. a preparation method for double wave length fluorescent and dual wavelength electrogenerated chemiluminescence(ECL) carbon quantum dot, is characterized in that, processing step is:
(1) be that the two to mix and this biased sample is put into stainless cylinder of steel by the ratio of 1:1 ~ 1:2 according to gac and the mass ratio of highly basic, the ratio being 1:50 ~ 1:70 according to the mass ratio of biased sample and Stainless Steel Ball takes Stainless Steel Ball and is added by Stainless Steel Ball in stainless cylinder of steel, wherein the cumulative volume of biased sample and Stainless Steel Ball accounts for 1/4 ~ 1/2 of stainless steel tank volume, with the rotating speed ball milling 40 ~ 70 hours of 400 ~ 600 revs/min;
(2) after ball milling step (1) obtained, sample dispersion is in deionized water, wherein, after ball milling, the mass ratio of sample and deionized water is 1:40 ~ 1:60, ultrasonic disperse 10 ~ 30 minutes, then being neutralized to pH with strong acid solution is 7.0, with the rotating speed of 5000 ~ 9000 revs/min, get supernatant liquor in super filter tube, with the centrifugation of high molecular weight cut-off super filter tube, get filtrate with the further centrifugation of low catching molecular super filter tube, and add deionized water wash 5 ~ 8 times, until filtrate is become colorless by yellow, get and retain part for orange-yellow carbon quantum dot solution.
2. preparation method according to claim 1, is characterized in that, highly basic described in step (1) is any one in potassium hydroxide or sodium hydroxide.
3. preparation method according to claim 1, is characterized in that, strong acid described in step (2) is any one in nitric acid, hydrochloric acid or sulfuric acid, and its concentration is 0.1 ~ 0.3mol L
-1.
4. preparation method according to claim 1, it is characterized in that, described in step (2), the molecular weight cut-off of high molecular weight cut-off super filter tube is 30,50 or 100kDa in one, the molecular weight cut-off of low catching molecular super filter tube be 3 or 10kDa in one, high molecular weight cut-off super filter tube and low catching molecular super filter tube are combined, to obtain the carbon quantum dot of different size.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074121A (en) * | 2022-06-27 | 2022-09-20 | 东南大学 | Preparation method of electrochemiluminescence wavelength-adjustable carbon quantum dot |
| CN115418225A (en) * | 2022-07-13 | 2022-12-02 | 齐鲁工业大学 | Phosphorus-doped modified carbon quantum dot and preparation method of composite photocatalyst thereof |
| WO2023229776A1 (en) * | 2022-05-26 | 2023-11-30 | University Of Tennessee Research Foundation | Synthesis and application of lignin-based carbon materials |
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| CN101973541A (en) * | 2010-10-11 | 2011-02-16 | 福州大学 | Method for extracting carbon quantum dots from activated carbon |
| CN103265020A (en) * | 2013-05-27 | 2013-08-28 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene quantum dot powder on large scale |
| JP2014133685A (en) * | 2013-01-11 | 2014-07-24 | National Institute Of Advanced Industrial & Technology | Method of producing carbon quantum dot and carbon quantum dot |
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| CN101973541A (en) * | 2010-10-11 | 2011-02-16 | 福州大学 | Method for extracting carbon quantum dots from activated carbon |
| JP2014133685A (en) * | 2013-01-11 | 2014-07-24 | National Institute Of Advanced Industrial & Technology | Method of producing carbon quantum dot and carbon quantum dot |
| CN103265020A (en) * | 2013-05-27 | 2013-08-28 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene quantum dot powder on large scale |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023229776A1 (en) * | 2022-05-26 | 2023-11-30 | University Of Tennessee Research Foundation | Synthesis and application of lignin-based carbon materials |
| CN115074121A (en) * | 2022-06-27 | 2022-09-20 | 东南大学 | Preparation method of electrochemiluminescence wavelength-adjustable carbon quantum dot |
| CN115418225A (en) * | 2022-07-13 | 2022-12-02 | 齐鲁工业大学 | Phosphorus-doped modified carbon quantum dot and preparation method of composite photocatalyst thereof |
| CN115418225B (en) * | 2022-07-13 | 2023-06-09 | 齐鲁工业大学 | Preparation method of phosphorus doped modified carbon quantum dot and composite photocatalyst thereof |
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