CN105131948B - Metal doped carbon points with high fluorescence quantum yield and preparation method and application thereof - Google Patents
Metal doped carbon points with high fluorescence quantum yield and preparation method and application thereof Download PDFInfo
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Abstract
The present invention provides metal doped carbon points with high fluorescence quantum yield and a preparation method and application thereof. The pure metal-doped carbon points are primarily synthesized by hydrothermal synthesis method, and the pure metal-doped carbon points have high fluorescence quantum yield. The pure metal-doped carbon points can be prepared only by one-step reaction, the cost is low, reaction speed is quick, byproducts and intermediate products are fewer; at the same time the pure metal-doped carbon points have the characteristics of high fluorescence quantum yield, are expected to be used in human blood trace Fe<3+> detection, and have broad application prospects in biological detection and sewage treatment.
Description
Technical field
The present invention relates to field of nanometer material technology, and in particular to a kind of metal-doped carbon point and its preparation method and application, especially
It is related to a kind of Copper-cladding Aluminum Bar carbon point with high-fluorescence quantum yield and its preparation method and application.
Background technology
Carbon has various electron orbit characteristic (sp, sp2、sp3), therefore many structures can be formed and property is strange
Special material, such as CNT, fullerene, Nano diamond, Graphene and graphene oxide.The reported firsts such as Xu in 2004
Carbon point, they are in the carbon ash produced from arc discharge using gel electrophoresis during separating single-wall CNT, it was found that have
The carbon nano-particles of fluorescence property, opened up novel fluorescence sensitive material new era (referring to X.D.Xu, R.Ray, Y.L.Gu,
et al.Electrophoretic Analysis and Purification of Fluorescent Single-
walledcarbon Nanotube Fragments[J],Jam Chem Soc,2004,126(40):12736-12737)。
Luminous carbon point (Carbon dots, CDs) is the spherical nanometer of the 10nm of being smaller in size than with carbon as skeleton structure
Particle.Used as a kind of new fluorescent nano material, carbon point not only has the fluorescence property similar to semiconductor-quantum-point, also has
Toxic low and good biocompatibility advantage.Additionally, carbon point also has and preparing simple, low cost and easily realizing extensive raw
The advantages of product.Therefore, carbon point has wide application front in fields such as cell marking, cell imaging, medical diagnosis, analysis detections
Scape.
The raw material of carbon point is cheap and easy to get, but many fluorescence of carbon point synthesized as carbon source using different raw materials are very
It is weak, even without fluorescence.In order to improve the luminous intensity of gained carbon point, its application in fields such as cell markings is widened, selected
Select suitable carbon source and effectively improve the preparation method of luminous intensity, it is simple to prepare the high carbon point of good water solubility and luminous intensity still
There is very big exploration space, wherein element doping is a kind of effective method for improving fluorescence intensity.
In the carbon point of doping, current research is concentrated mainly on sulphur, the doping of nitrogen monad or diatomic doping
On carbon point, such as CN104726098A discloses a kind of sulphur, the carbon quantum dot of nitrogen codope high-fluorescence quantum yield, wherein, carbon
The carbon source of quantum dot is provided by sodium citrate, and sulphur source and nitrogen source are all provided by sulphamide, by dissolution of raw material in hydrothermal reaction kettle
Reaction, after product natural cooling to be synthesized isolated solution is carried out, and high-fluorescence quantum yield is just obtained after solution is dried
Sulphur, nitrogen codope carbon quantum dot；CN104449693A discloses a kind of preparation method of the fluorescent carbon quantum dot of nitrogen sulfur doping, its
It is that, with citric acid as carbon source, GSH is nitrogen sulfur doping agent, is reaction platform by micro-wave oven, heating is prepared with fluorescence
The carbon quantum dot of performance, by dialysis and freeze-drying removal of residue and moisture are removed, and obtain quantum dot powder.Although with sulphur,
Nitrogen monad adulterates or the carbon point of diatomic doping has higher luminous intensity, however, its fluorescence quantum yield is still
Remain at low levels, and, it there is also larger limitation in terms of biological detection and sewage disposal.
Therefore, how to research and develop one kind and there is more high-fluorescence quantum yield, make gained carbon point luminous intensity higher and expand it
The carbon point of application has become current problem demanding prompt solution.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of metal-doped carbon point and its preparation method and application, special
Ti Gongliao not a kind of Copper-cladding Aluminum Bar carbon point with high-fluorescence quantum yield and its preparation method and application.The present invention passes through copper doped
Atom changing the band structure inside carbon point, so as to prepare a kind of point of the carbon with high-fluorescence quantum yield, and by its
For Fe3+In detection or sewage disposal.
It is, up to this purpose, to present invention employs following technical scheme：
In a first aspect, the invention provides a kind of preparation method of metal-doped carbon point, its adopt hydro-thermal method, microwave method or
Plasma partition method prepares the metal-doped carbon point.
Metal-doped carbon point in the present invention, it is preferred to use hydro-thermal method is prepared.
Heretofore described metal can select copper or zinc, preferably copper.
The present invention carries out the preparation of Copper-cladding Aluminum Bar carbon point using hydro-thermal method, and it needs single step reaction, and reaction speed is very fast, and
Accessory substance and intermediate product are few, and raw material dosage is few, low cost.
In the present invention, due to the electron orbit characteristic of the metallic elements such as copper, have compared with nonmetalloids such as sulphur, nitrogen and more enliven
Outermost layer mobile electron, easily there is metalline and change, with bigger research potential.For example disclosed in CN103058274A
A kind of method of Copper-cladding Aluminum Bar titanium oxide, the change arranged by the electron orbit of metallic copper and energy level transition, are substantially increased
Photoelectric transformation efficiency.The doping of the single metal of copper is more easy to realize quantitative tune compared to the sulphur nitrogen codope in CN104312582A
Control, becomes the basis of bimetal-doped research.Therefore single metallic copper doped carbon point is adopted in the present invention, obtained carbon can be made
Point has higher fluorescence quantum yield, and the luminous intensity of the carbon point is higher.
The preparation method of heretofore described Copper-cladding Aluminum Bar carbon point, specifically includes following steps：
(1) carbon source and Tong Yuan are dissolved in the water, obtain precursor solution；
(2) precursor solution is reacted in hydrothermal reaction kettle, is subsequently cooled to room temperature and obtains suspension；
(3) suspension is separated, obtains solution；
(4) solution is dried, obtains the Copper-cladding Aluminum Bar carbon point.
In the present invention, step (1) carbon source is sodium citrate or citric acid, preferably sodium citrate.
Copper source is stannous chloride and/or copper sulphate, preferably stannous chloride.
In the present invention, the concentration of carbon source is 0.01mol/L-0.1mol/L in step (1) precursor solution, for example may be used
Be 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L,
0.1mol/L；Preferably, the concentration in copper source is 0.001-1mol/L in the precursor solution, for example, can be 0.001mol/
L、0.002mol/L、0.005mol/L、0.010mol/L、0.015mol/L、0.020mol/L、0.025mol/L、0.030mol/
L, 0.060mol/L, 0.150mol/L, 0.250mol/L, 0.400mol/L, 0.600mol/L, 0.800mol/L, 1mol/L, it is excellent
Elect 0.025mol/L as.The mol ratio of i.e. heretofore described sodium citrate and stannous chloride is 1:0.1-1:10, for example can be with
It is 1:0.1、1:0.25、1:0.5、1:1、1:2、1:5、1:8 etc., preferably 1:0.25.
If the mol ratio of sodium citrate and stannous chloride is 1:Less than 0.25, its fluorescence intensity does not have significantly increasing
Plus；If sodium citrate solution is more than 1 with the mol ratio of the cuprous chloride solution:After 0.25, fluorescence intensity drastically declines, and rubs
You are than being 1:When 0.25, there is peak value in fluorescence intensity.The preferably sodium citrate of the invention and the mol ratio of stannous chloride are 1:
0.25, to guarantee to possess optimal fluorescent effect.
In the present invention, step (1) solution is to be completely dissolved.
Heretofore described hydrothermal reaction kettle is the stainless steel autoclave of teflon lined.
In the present invention, step (2) reaction temperature is 120-240 DEG C, for example can be 120 DEG C, 140 DEG C, 160 DEG C,
180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, preferably 190 DEG C -210 DEG C.In the temperature range
Can Copper-cladding Aluminum Bar carbon point of the synthesis with fluorescence property.
Preferably, the reaction time be more than 2h, for example can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h,
11h, 12h, preferably 6h.
In the present invention, step (3) separation is carried out using separator-filter.
Preferably, the separator-filter is cylindrical membrane separator-filter.
It is further preferred that the cylindrical membrane separator-filter is molecular cut off 3kDa, 5kDa, 10kDa or 30kDa
In any one or at least two combination.
In the present invention, step (4) drying is carried out under vacuum.
Preferably, the temperature of the drying is -100-100 DEG C, for example can be -100 DEG C, -90 DEG C, -80 DEG C, -60
℃、-50℃、-20℃、10℃、50℃、80℃、100℃；The dry time be 3-24h, for example can be 3h, 5h, 6h, 8h,
10h、12h、15h、18h、20h、24h。
Used as currently preferred technical scheme, the preparation method of the Copper-cladding Aluminum Bar carbon point comprises the steps：
(1) sodium citrate and stannous chloride are dissolved in the water, obtain precursor solution；
(2) precursor solution is reacted into more than 2h in hydrothermal reaction kettle, then naturally cools to room temperature and obtain suspension；
(3) suspension is separated with cylindrical membrane separator-filter, obtains solution；
(4) solution is dried, obtains the Copper-cladding Aluminum Bar carbon point；
Wherein, the concentration of sodium citrate is 0.1mol/L in the precursor solution, and the concentration of stannous chloride is
0.025mol/L。
Second aspect, present invention also offers the metal-doped carbon point that the method according to first aspect is prepared.
The metal-doped carbon point luminous intensity that the present invention is obtained is high, and fluorescence quantum yield is high.
The third aspect, present invention also offers the purposes of the metal-doped carbon point according to second aspect, by the gold
Category doped carbon point is used for Fe3+Detection or sewage disposal.
Therefore, the invention provides the metal-doped carbon point as described in second aspect is used for Fe3+Detection or sewage disposal
Purposes (method).When for Fe3+During detection, its minimum detectability can reach 0.1nmol/L.
Compared with the prior art, the present invention has the advantages that：
(1) the Copper-cladding Aluminum Bar carbon point prepared using the method for the present invention, only needs single step reaction, and reaction speed is very fast, and secondary
Product and intermediate product are few, and raw material dosage is few, low cost.
(2) the Copper-cladding Aluminum Bar carbon point that the present invention is prepared, its fluorescence quantum yield is high, reaches as high as 70.81%；Gained
Carbon point luminous intensity is high, and is successfully applied to Fe3+Detection so that Fe3+The minimum of detection can reach 0.1nmol/L；This
Outward, also have broad application prospects at the aspect such as biological detection and sewage disposal.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of Copper-cladding Aluminum Bar fluorescent carbon point prepared by the embodiment of the present invention 1；
Fig. 2 is the luminous intensity comparison diagram of Copper-cladding Aluminum Bar fluorescent carbon point prepared by the embodiment of the present invention 1 and general carbon point, in figure
300-400nm is general carbon point, and 400-550nm is Copper-cladding Aluminum Bar carbon point, and light source is 340nm ultraviolet lights；
Fig. 3 is the C of Copper-cladding Aluminum Bar fluorescent carbon point prepared by the embodiment of the present invention 11sSwarming collection of illustrative plates；
Fig. 4 is the Cu swarming collection of illustrative plates of Copper-cladding Aluminum Bar fluorescent carbon point prepared by the embodiment of the present invention 1；
Fig. 5 is the O of Copper-cladding Aluminum Bar fluorescent carbon point prepared by the embodiment of the present invention 11sSwarming collection of illustrative plates；
Fig. 6 is the FTIR collection of illustrative plates of Copper-cladding Aluminum Bar fluorescent carbon point prepared by the embodiment of the present invention 1；
Fig. 7 is the Fe of 50 μM of addition3+The luminous intensity of carbon point relation over time after solution；
Fig. 8 is different Fe3+The luminous intensity of carbon point under concentration (0,1,20,50,70,100,200 μM)；
Fig. 9 is the pad value and Fe of luminous intensity3+The relation of concentration；
Figure 10 is added after different metal ions, the pad value of luminous intensity of the carbon point at 440nm.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
A () takes the sodium citrate of 0.735g and 0.0617g stannous chlorides, be dissolved in 25mL deionized waters and be sufficiently stirred for
5min, obtains precursor solution；
B () is placed in the precursor solution for obtaining in the stainless steel autoclave of 50ml teflon lineds, after sealing
Temperature naturally cools to room temperature to react 6h under conditions of 200 DEG C, obtains suspension；
C suspension with being filtered with molecular cut off 3kDa cylindrical membrane separator-filters, is collected filtered solution by (), do
The dry Copper-cladding Aluminum Bar carbon point for obtaining high fluorescent yield.
Referring to Fig. 1, it is the transmission electron microscope picture of Copper-cladding Aluminum Bar fluorescent carbon point manufactured in the present embodiment, and from Fig. 1 tests carbon is obtained
The uniform round particle of presentation of point, between 2.5nm to 5nm, average grain diameter is 3.76nm to size.
Referring to Fig. 2, it is Copper-cladding Aluminum Bar fluorescent carbon point manufactured in the present embodiment and the sulfur doping disclosed in CN104312582A
Carbon quantum dot as general carbon point luminous intensity comparison diagram, from this figure, it can be seen that the Copper-cladding Aluminum Bar that embodiment 1 is prepared is glimmering
The luminous intensity of light carbon point is apparently higher than general carbon point (i.e. sulfur doping carbon quantum dot disclosed in CN104312582A).
It is the XPS swarming collection of illustrative plates of Copper-cladding Aluminum Bar fluorescent carbon point manufactured in the present embodiment referring to Fig. 3-7, as can be seen from the figure copper
There is the presence of Cu-C keys in doped carbon point.
Embodiment 2
A () takes the sodium citrate of 0.735g and 0.0617g stannous chlorides, be dissolved in 25mL deionized waters and be sufficiently stirred for
5min, obtains precursor solution；
B () is placed in the precursor solution for obtaining in the stainless steel autoclave of 50mL teflon lineds, after sealing
6h is reacted under conditions of 200 DEG C, room temperature is naturally cooled to, suspension is obtained；
C () is filtered to suspension with molecular cut off 3kDa cylindrical membrane separator-filters, collect filtered solution, is dried
Obtain the Copper-cladding Aluminum Bar carbon point of high fluorescent yield.The carbon point that the present embodiment is obtained luminous intensity under 340nm light irradiations is 350000.
Embodiment 3
A () takes the sodium citrate of 0.735g and 0.0617g stannous chlorides, be dissolved in 25mL deionized waters and be sufficiently stirred for
5min, obtains precursor solution；
B () is placed in the precursor solution for obtaining in the stainless steel autoclave of 50mL teflon lineds, close at 180 DEG C
6h is reacted under conditions of envelope, room temperature is naturally cooled to, suspension is obtained；
C () to filtering to suspension, collects filtered solution with molecular cut off 5kDa cylindrical membranes separator-filter, dry
To a kind of Copper-cladding Aluminum Bar carbon point of high fluorescent yield.The carbon point that the present embodiment is obtained luminous intensity under 450nm light irradiations is
140000。
Embodiment 4
A () takes the sodium citrate of 0.735g and 0.0617g stannous chlorides, be dissolved in 25mL deionized waters and be sufficiently stirred for
5min, obtains precursor solution；
B () is placed in the precursor solution for obtaining close at 200 DEG C in the stainless steel autoclave of 50mL teflon lineds
10h is reacted under conditions of envelope, room temperature is naturally cooled to, suspension is obtained；
C () is filtered with the cylindrical membrane separator-filter of molecular cut off 3kDa to suspension, collection filtered solution, dry
To a kind of high photoluminescence intensity carbon point.The carbon point that the present embodiment is obtained luminous intensity under 440nm light irradiations is 200000.
Embodiment 5
Copper-cladding Aluminum Bar carbon point in the present invention is used successfully to Fe3+Detection.10 μ L carbon point deionized waters are diluted to into 1mL,
After being excited with the light of wavelength 340nm, the luminous intensity at 440nm is denoted as into initial strength F0.Add in the solution and contain Fe3+
Solution, luminous intensity is surveyed after 1min, be denoted as F1.Δ F is Fe3+Detection signal, expression formula be Δ F=F0-F1.Excite crack
Width and transmite slit width are respectively 5nm and 5nm.Fig. 7-10 is the carbon point to Fe3+Sensitiveness experimental result.
Wherein, Fig. 7 is the Fe of 50 μM of addition3+The luminous intensity of carbon point relation over time after solution.Luminous intensity
It is almost unchanged after 1min, therefore luminous intensity is detected after 1min in testing.Fig. 8 is different Fe3+Concentration (0,1,20,50,
70th, 100,200 μM) under carbon point luminous intensity.Luminous intensity is with Fe3+The increase of concentration is decreased obviously.Fig. 9 is luminous intensity
Pad value and Fe3+The relation of concentration.Work as Fe3+In the range of 1-2000nM, the two is in strong linear relationship, coefficient correlation for concentration
0.9967.Then calculated according to triple standard difference method, detection is limited to 0.1nmol/L, better than Fe before3+Detection report (Liu Y,
Xiao N,Gong N,Wang H,Shi X,Gu W,et al.One-step microwave-assisted
polyolsynthesis of green luminescent carbon dots as optical
nanoprobes.Carbon.2014；68:258-64；Ju J,Chen W.Synthesis of highly fluorescent
nitrogen-doped graphene quantum dots for sensitive,label-free detection of Fe
(III)in aqueous media.Biosens Bioelectron.2014；8:219-25；Zhu S,Meng Q,Wang L,
Zhang J,Song Y,Jin H,et al.Highly photoluminescent carbon dots for multicolor
patterning,sensors,and bioimaging.Angew Chem Int Ed Engl.2013；52(14):3953-7).
Figure 10 is added after different metal ions, the pad value of luminous intensity of the carbon point at 440nm.Add 200 μM of Fe3+Solution
Afterwards, luminous intensity is decreased obviously, and the impact of other metal ions almost can be ignored.This shows the Copper-cladding Aluminum Bar carbon in the present invention
Point detection Fe3+There is good selectivity.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, the equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (15)
1. a kind of preparation method of metal-doped carbon point, it is characterised in that it is described metal-doped that it adopts hydro-thermal method to prepare
Carbon point；The metal is copper；
Methods described comprises the steps：
(1) carbon source and Tong Yuan are dissolved in the water, obtain precursor solution；
(2) precursor solution is reacted in hydrothermal reaction kettle, is subsequently cooled to room temperature and obtains suspension；
(3) suspension is separated, obtains solution；
(4) solution is dried, obtains Copper-cladding Aluminum Bar carbon point；
The carbon source is sodium citrate；Copper source is stannous chloride；The sodium citrate is 1 with the mol ratio of stannous chloride:
0.25。
2. method according to claim 1, it is characterised in that the concentration of carbon source is in step (1) precursor solution
0.01mol/L-0.1mol/L。
3. method according to claim 1, it is characterised in that the concentration in copper source is in step (1) precursor solution
0.001-1mol/L。
4. method according to claim 3, it is characterised in that the concentration in copper source is in step (1) precursor solution
0.025mol/L。
5. method according to claim 1, it is characterised in that the temperature of step (2) reaction is 120-240 DEG C.
6. method according to claim 1, it is characterised in that the time of step (2) reaction is more than 2h.
7. method according to claim 6, it is characterised in that the time of step (2) reaction is 6h.
8. method according to claim 1, it is characterised in that step (3) separation is carried out using separator-filter.
9. method according to claim 8, it is characterised in that the separator-filter is cylindrical membrane separator-filter.
10. method according to claim 9, it is characterised in that the cylindrical membrane separator-filter is molecular cut off
In 3kDa, 5kDa, 10kDa or 30kDa any one or at least two combination.
11. methods according to claim 1, it is characterised in that step (4) drying is carried out under vacuum.
12. methods according to claim 1, it is characterised in that the temperature of step (4) drying is -100～100 DEG C,
The time of the drying is 3-24h.
13. methods according to claim 1, it is characterised in that comprise the steps：
(1) sodium citrate and stannous chloride are dissolved in the water, obtain precursor solution；
(2) precursor solution is reacted into more than 2h in hydrothermal reaction kettle, then naturally cools to room temperature and obtain suspension；
(3) suspension is separated with cylindrical membrane separator-filter, obtains solution；
(4) solution is dried, obtains Copper-cladding Aluminum Bar carbon point；
Wherein, the concentration of sodium citrate is 0.1mol/L in the precursor solution, and the concentration of stannous chloride is 0.025mol/L.
The metal-doped carbon point that 14. methods according to any one of claim 1-13 are prepared.
The purposes of 15. metal-doped carbon points according to claim 14, it is characterised in that use the metal-doped carbon point
In Fe3+Detection or sewage disposal.
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| CN105647528B (en) * | 2016-02-02 | 2018-09-11 | 中国石油大学(北京) | A kind of zinc doping carbon quantum dot, preparation method and its application in detection field |
| CN105664955B (en) * | 2016-03-21 | 2017-12-05 | 中国石油大学(华东) | A kind of preparation method of the metal co-doped carbon quantum dot of copper zinc |
| CN105860967B (en) * | 2016-04-15 | 2017-12-01 | 安徽师范大学 | Fluorescent carbon point and preparation method thereof and the monitoring method of catalysis p-nitrophenol degraded |
| CN106281319B (en) * | 2016-07-25 | 2018-01-12 | 桂林理工大学 | The preparation method of fluorescence carbon nano-particle based on stratiform transition metal carbide |
| CN106367065B (en) * | 2016-08-26 | 2018-09-25 | 广西师范大学 | The preparation method and its usage of copper, nitrogen-doped carbon quantum dot with dual light treatment effect and fluorescence imaging |
| CN106566540B (en) * | 2016-10-21 | 2019-01-22 | 中国科学院长春光学精密机械与物理研究所 | A kind of nitrogen, sulphur, copper codope carbon nano dot and the preparation method and application thereof |
| CN106893585B (en) * | 2017-02-16 | 2020-04-28 | 四川省人民医院 | Metal manganese doped carbon quantum dot with high fluorescence quantum yield and preparation method and application thereof |
| CN107573930A (en) * | 2017-10-13 | 2018-01-12 | 西南大学 | A kind of preparation method of double transmitting fluorescent carbon points |
| CN108165268B (en) * | 2018-01-19 | 2020-12-08 | 北京服装学院 | Preparation of copper ion doped carbon quantum dot, obtained carbon quantum dot and application |
| CN108384537B (en) * | 2018-01-19 | 2021-02-26 | 北京服装学院 | Preparation of barium ion doped carbon quantum dot, obtained carbon quantum dot and application |
| CN108251107B (en) * | 2018-01-19 | 2021-01-05 | 北京服装学院 | Preparation of cobalt ion doped carbon quantum dot, obtained carbon quantum dot and application |
| CN108318438B (en) * | 2018-01-19 | 2021-10-01 | 广东工业大学 | Silver-doped fluorescent carbon quantum dot, preparation method thereof and cholesterol detection method |
| CN111714632A (en) * | 2020-06-28 | 2020-09-29 | 南宁师范大学 | Preparation method and application of phthalocyanine nanoparticles |
| CN112961669A (en) * | 2021-02-01 | 2021-06-15 | 苏州星烁纳米科技有限公司 | Preparation method of solid-phase carbon quantum dot, solid-phase carbon quantum dot prepared by same and light-emitting device |
| CN114214068B (en) * | 2022-01-19 | 2024-01-26 | 合肥学院 | Preparation method of metal-doped fluorescent biomass carbon quantum dot |
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| CN104312582A (en) * | 2014-09-18 | 2015-01-28 | 中国石油大学(北京) | Sulfur doped carbon quantum dot with high fluorescent quantum yield, and preparation method and application thereof |
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