CN110079308A - A kind of nitrogen, the sulphur of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method - Google Patents
A kind of nitrogen, the sulphur of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 128
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000005864 Sulphur Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims abstract description 16
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims abstract description 16
- 229960002989 glutamic acid Drugs 0.000 claims abstract description 16
- 229930182817 methionine Natural products 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000010792 warming Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 238000002189 fluorescence spectrum Methods 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000003763 carbonization Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FFFHZYDWPBMWHY-VKHMYHEASA-N L-homocysteine Chemical compound OC(=O)[C@@H](N)CCS FFFHZYDWPBMWHY-VKHMYHEASA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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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- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Nitrogen, the sulphur that the present invention discloses a kind of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method, belong to carbon quantum dot technical field.The present invention takes glutaminol and methionine to mill in agateware after mixing according to a certain percentage, is laid in beaker bottom, is then at the uniform velocity warming up to 200~300 DEG C, and heat 5~20min of reaction in this temperature range and obtain reaction product A；Reaction product A is cooled to room temperature, then passivator is added to be uniformly mixed in reaction product A and obtains mixed solution B；Mixed solution B is heated to 2~10min of reaction under the conditions of 200~300 DEG C and obtains mixed solution C；Mixed solution C is cooled to room temperature, centrifugal treating is carried out, dialyses after standing through bag filter and remove unreacted raw material and impurity, obtain nitrogen, the fluorescent carbon quantum dot that sulphur is co-doped with.Preparation process of the invention is simply controllable, by changing preparation condition or passivator, that is, controllable carbon quantum dot wavelength of fluorescence, is allowed to cover green light, yellow light and red spectral band, to meet the needs of practical application.
Description
Technical field
The present invention relates to nitrogen, the sulphur of a kind of adjustable wavelength of fluorescence to be co-doped with carbon quantum dot preparation method, belongs to carbon quantum dot skill
Art field.
Background technique
Carbon quantum dot (carbon quantum dots, CQDs) is the carbon nanomaterial of discovery in 2004, is nano material
Rising star, it has superior fluorescent characteristic, unique chemistry, electronics and optical property.With traditional dye molecule and semiconductor
Quantum dot is compared, it not only has good light resistance and scintillation light bleachability, also low, the at low cost, bio-compatible with toxicity
The important features such as property and good light stability.Therefore, CQDs can be widely applied to opto-electronic device, energy conversion, photocatalysis, sensing
The numerous areas such as device, bio-imaging, cell marking and drug delivery, and application potential is huge, has a extensive future, by academia
It is paid close attention to industrial circle, relevant research and application also rapidly become full of vitality and high speed development frontier.
Fluorescent carbon quantum dot can be prepared there are many method at present, as electrochemical oxidation process, hydro-thermal patterning method and carbonization have
Machine object etc..Wherein pyrolysis organic synthesis carbon quantum dot is by fluorescence probe pyrolysis carbonization into carbon quantum dot, thus this
Class method can realize the size controllable preparation of carbon quantum dot by control reaction condition, make carbon quantum dot can be with large-scale production
And it is artificial controllable.However, the carbon quantum dot impurity for using biomass or organic matter to synthesize for carbon source in the prior art is more, usually
In the case of carbon quantum dot fluorescence quantum yield obtained be lower than 50%, separating-purifying is difficult, leads to carbon quantum dot production cost
Increase.In addition, its fluorescence emission wavelengths majority concentrates on bluish-green optical band, the application range of carbon quantum dot is significantly limited.
Experiment and theoretical research have confirmed that the doping of carbon quantum dot and surface/edge modification can effectively improve carbon
The photoelectric properties of quantum dot.Carbon quantum dot doping is primarily referred to as the foreign atoms such as nitrogen, sulphur, phosphorus mixing carbon quantum dot carbon core region
Graphene skeleton in, will occur surface and marginality energy level in the carbon quantum dot forbidden band after doping, and be similarly to semiconductor
Impurity energy level, their presence cause the physicochemical properties such as the fluorescent characteristic of carbon quantum dot, reactivity, catalytic performance significant
Variation.Therefore, passivator is commonly used to disperse carbon quantum dot, makes carbon quantum dot edge absorption largely base corresponding with passivator
Group, to change carbon quantum dot fluorescence property, change its wavelength of fluorescence with excitation wavelength, i.e., carbon quantum dot fluorescence and swash
It encourages unrelated.In addition, can effectively induce the electronics in carbon quantum dot conduction band by being passivated to carbon quantum dot edge, increase carbon
The surface energy of quantum dot, prevents fluorescence decay caused by due to carbon quantum dot is as reunion to be even quenched, to enhance carbon quantum
Point fluorescence property and stability, extend the holding time of carbon quantum dot, to meet the needs of practical application.
For example, being doped by agent containing ammonia to carbon quantum dot, amino is introduced at carbon quantum dot edge or in carbon quantum dot
Sp2Region introduces pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen (including C in the form of nitrogen atom doping3- N and C2- N-H), it is acquired
Nitrogen-doped carbon quantum dot show higher fluorescence quantum yield or photocatalytic activity；Using polyvinyl alcohol as carbon source, by dense
Sulfuric acid dehydration carbonization and washing, purifying technique obtain sulfur doping carbon quantum dot；By phenthazine, sodium nitrite, methylene chloride and
Acetic acid mixing, occurs nitration reaction, obtains 3,7- dinitro phenthazine；3,7- dinitro phenthazine and lye are mixed, successively
Hydro-thermal reaction is carried out, dialysis obtains sulphur, the carbon quantum dot that nitrogen is co-doped with；Using glucose as carbon source, homocysteinic acid is nitrogen, sulphur
Impurity source prepares nitrogen, sulphur is co-doped with carbon quantum dot；Using the plant fruit rich in various plants albumen as raw material, by reaction kettle
Middle carry out hydro-thermal reaction, prepares nitrogen, sulphur is co-doped with carbon quantum dot.Currently, the method for preparation doping carbon quantum dot is numerous, but still
There are two critical issues: (1) since conventional hydro-thermal method carbonization lead to the doping that in reaction solution remains a large amount of high-dissolvabilities,
The doping concentration eventually led in carbon quantum dot is lower；It (2) is forerunner with the mixture of the plurality of raw materials such as carbon source, nitrogen source, sulphur source
Body realizes carbon quantum dot doping, and preparation cost is expensive, and preparation process is complicated, and impurity is more, is not easy to large-scale production and preparation, because
And effectively atom doped method report is very few at present.It is therefore necessary to develop simple and effective, low cost and high yield preparative
The method of doping fluorescent carbon quantum dot that can be excellent.
Summary of the invention
It is asked for the carbon quantum dot toxicity that carbon quantum dot preparation process is cumbersome, nitrogen and sulphur are co-doped with of doping in the prior art is big etc.
Topic, the present invention provide one kind using methionine and glutaminol as presoma, and a step pyrolysismethod prepares nitrogen, sulphur is co-doped with carbon quantum dot
Method.The present invention can be achieved doped carbon quantum dot fluorescence launch wavelength tuning: (1) by regulate and control pyrolytic reaction time come
Adjust carbonizing degree；(2) nitrogen/sulphur atom doping is adjusted by the usage ratio of regulation methionine and glutaminol；
(3) using water, alcohol, oxalic acid, sodium hydroxide etc. as passivator, enhance the fluorescence property of carbon quantum dot.Preparation method green
Environmentally friendly, safe and simple, the carbon quantum dot fluorescence property being prepared is good, and launch wavelength can be adjusted to feux rouges wave from green wavelength
Long range.
A kind of nitrogen, the sulphur of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method, the specific steps are as follows:
(1) glutaminol and methionine are milled after mixing, is laid in reaction container bottom, then at the uniform velocity heats up
To 200~300 DEG C, and mixture carbonization, discoloration of the 5~20min of reaction into container are heated in this temperature range and is reacted
Product A；
(2) step (1) reaction product A is cooled to room temperature, passivator is added in reaction product A uniformly mixed obtain
Mixed solution B；
(3) the mixed solution B in step (2) is placed in 2~10min of heating reaction under the conditions of temperature is 200~300 DEG C again
Obtain mixed solution C；
(4) mixed solution C of step (3) is cooled to room temperature, carries out centrifugal treating, dialyses and remove through bag filter after standing
Unreacted raw material and impurity obtain nitrogen, sulphur is co-doped with carbon quantum dot.
The ratio of glutaminol and methionine is (1~3): (1~3) in the step (1).
Step (2) passivator is ethyl alcohol, deionized water, oxalic acid solution or sodium hydroxide solution.
Further, the ethyl alcohol is to analyze pure, and the concentration of oxalic acid solution is 3~10g/L, sodium hydroxide solution it is dense
Degree is 3~10g/L.
The volume ratio of step (2) passivator and reaction product A are (10~20): 1.
The revolving speed of step (4) centrifugal treating is 12000r/min, and the time of centrifugal treating is 20min.
The molecule interception of step (4) bag filter is 100~300k Da.
Beneficial effects of the present invention:
(1) using glutaminol and methionine as raw material, nitrogen, the sulphur prepared by simple pyrolytic reaction is co-doped with the present invention
Carbon quantum dot, advantages of nontoxic raw materials, cheap and easy to get, preparation cost is low, and preparation process is simply controllable, short preparation period；
(2) nitrogen prepared by the present invention, sulphur are co-doped with carbon quantum dot fluorescence quantum yield height, and size dispersion is uniform, tool water solubility,
Photostability is strong, biocompatibility and low cytotoxicity, can be applied to cell marking, bio-imaging, fluorescence probe, luminescence generated by light
Equal numerous areas；
(3) it is raw material that the present invention, which selects glutaminol and methionine, and the nitrogen prepared by simple pyrolytic reaction, sulphur are total
Carbon dope quantum dot can adjust carbonizing degree by regulating and controlling the time of pyrolytic reaction；Pass through regulation methionine and glutaminol
Usage ratio so as to adjust nitrogen/sulphur atom doping；Using water, alcohol, oxalic acid, sodium hydroxide etc. as passivator, enhancing
The fluorescence property of carbon quantum dot；The fluorescence emission wavelengths that final nitrogen, the sulphur for realizing that the present invention is prepared is co-doped with carbon quantum dot can
Tuning, fluorescence emission wavelengths cover green light, yellow light and red spectral band.
Detailed description of the invention
Fig. 1 is the TEM picture and its particle diameter distribution of carbon quantum dot surface topography (a) prepared by embodiment 1 and lattice fringe (b)
Scheme (c)；
Fig. 2 is carbon quantum dot X-ray diffraction spectrogram prepared by embodiment 1；
Fig. 3 is carbon quantum dot x-ray photoelectron spectroscopy prepared by embodiment 1；
Fig. 4 is carbon quantum dot C 1s high resolution scanning spectrum prepared by embodiment 1；
Fig. 5 is carbon quantum dot N 1s high resolution scanning spectrum prepared by embodiment 1；
Fig. 6 is carbon quantum dot S 2p high resolution scanning spectrum prepared by embodiment 1；
Fig. 7 is the carbon quantum dot absorption spectra comparison diagram of Examples 1 to 4 preparation；
Fig. 8 is carbon quantum dot fluorescence Spectra prepared by embodiment 1；
Fig. 9 is carbon quantum dot fluorescence Spectra prepared by embodiment 2；
Figure 10 is carbon quantum dot fluorescence Spectra prepared by embodiment 3；
Figure 11 is carbon quantum dot fluorescence Spectra prepared by embodiment 4；
Figure 12 is carbon quantum dot absorption spectra comparison diagram prepared by embodiment 5~9；
Figure 13 is carbon quantum dot fluorescence Spectra prepared by embodiment 5；
Figure 14 is carbon quantum dot fluorescence Spectra prepared by embodiment 6；
Figure 15 is carbon quantum dot fluorescence Spectra prepared by embodiment 7；
Figure 16 is carbon quantum dot fluorescence Spectra prepared by embodiment 8；
Figure 17 is carbon quantum dot fluorescence Spectra prepared by embodiment 9；
Figure 18 is the carbon quantum dot chromatic diagram of Examples 1 to 9 preparation.
Specific embodiment
The present invention will be described in detail below with reference to specific embodiments, but protection scope of the present invention is not limited in described
Hold.
Embodiment 1
A kind of nitrogen, the sulphur of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method, the specific steps are as follows:
(1) it takes 2g glutaminol and 1g methionine to mill in agateware after mixing, is laid in beaker bottom,
Being subsequently placed on heating platform and being at the uniform velocity warming up to temperature is 200 DEG C, and mixed into beaker in 200 DEG C of heated at constant temperature reaction 5min
The dehydration of conjunction object, carbonization, discoloration obtain reaction product A；
(2) it is cooled to room temperature to the reaction product A in step (1), passivator (ethyl alcohol) is added in reaction product and is mixed
It closes and uniformly obtains mixed solution B；
(3) the mixed solution B in step (2) heated at constant temperature 3min on the platform that temperature is 200 DEG C is again placed in obtain
Mixed solution C；
(4) it is cooled to room temperature to the mixed solution C in beaker, carries out centrifugal treating, dialyse and remove through bag filter after standing
Unreacted raw material and other little particle impurity, obtain nitrogen, sulphur is co-doped with carbon quantum dot；Wherein the revolving speed of centrifugal treating is 8000r/
Min, the time of centrifugal treating are 10min；The volume ratio of passivator (ethyl alcohol) and reaction product C are 15:1；The molecule of bag filter
Interception is 100k Da；
Shown in carbon quantum dot surface topography picture manufactured in the present embodiment such as Fig. 1 (a), TEM picture such as Fig. 1 (b) of lattice fringe
Shown and its corresponding Fourier transformation (FFT) figure is as shown in illustration in (a), from Fig. 1 (a)~(b) it is found that carbon quantum dot has
Good dispersibility and crystallinity, lattice fringe is clear, and the spacing of crystal face is 0.28nm；The grain size distribution of carbon quantum dot is as schemed
Shown in 1 (c), from Fig. 1 (c) it is found that the size of carbon quantum dot is distributed as 3~8nm, average grain diameter 5.87nm；
Carbon quantum dot X-ray diffraction spectrum (XRD) manufactured in the present embodiment is as shown in Fig. 2, as can be seen from Figure 2, the X of carbon quantum dot
X ray diffraction map is Dan Kuanpu, and peak position is located at 31.2 ° in 2 θ, according to bragg's formula (2dsin θ=n λ, X-ray diffraction
Wavelength X=0.15406nm) d=0.2865nm can be calculated, correspond to graphite (002) interplanar distance, this and the crystalline substance in Fig. 1 (b)
Interplanar distance matches, this spacing is more bigger than usual graphite (002) interplanar distance 0.21nm, this is because carbon quantum dot be dispersed in it is blunt
In agent, its edge is made to adsorb the oxygen-containing groups such as a large amount of hydroxyl, carboxyl, carbonyl, the reason for causing interplanar distance to expand；XRD
Map does not occur impurity peaks, shows that the carbon quantum dot crystallinity being prepared is high；
The full spectrogram of carbon quantum dot x-ray photoelectron spectroscopy (XPS) manufactured in the present embodiment is as shown in figure 3, can from Fig. 3
Know, four at 284.8eV, 400.5eV, 532.8eV and 164.2eV peak is belonging respectively to carbon core sp2C 1s, the N in region
1s, O 1s and S 2p, analysis obtain four kinds of the surface composition elemental carbon, oxygen, nitrogen and sulphur atomic percent difference of the carbon quantum dot
It is 74.67%, 19.58%, 3.99% and 1.76%；
Carbon quantum dot C 1s high resolution scanning spectrum manufactured in the present embodiment is as shown in figure 4, N 1s high resolution scanning spectrum such as Fig. 5
Shown, S 2p high resolution scanning spectrum is as shown in fig. 6, from Fig. 4~6 it is found that high resolution scanning composes C 1s in 284.8eV, 286.8eV
The combination energy of C-C/C=C, C-O and O-C=O key is corresponded respectively to the peak position at 288.1eV；High resolution scanning spectrum N 1s exists
Peak position at 399.8eV, 400.75eV and 401.6eV corresponds respectively to Pyridinic N, Pyrrolic N and Amidic N.
High resolution scanning composes peak position of the S 2p at 164.0eV and 167.5eV and corresponds respectively to the peak S-C-S and C-SOx.
Embodiment 2
On the basis of embodiment 1, passivator is replaced with into sodium hydroxide solution, concentration 3.6g/L, other conditions
It is constant.
Embodiment 3
On the basis of embodiment 1, passivator is replaced with into oxalic acid solution, concentration 3.6g/L, other conditions are constant.
Embodiment 4
On the basis of embodiment 1, passivator is replaced with into deionized water, other conditions are constant；
The uv-visible absorption spectra (UV-Vis) of the carbon quantum dot of Examples 1 to 4 preparation is as shown in fig. 7, carbon quantum dot
Uv-visible absorption spectra absorption peak be focused on the UV light region 200~400nm；Carbon quantum dot prepared by embodiment 1 is glimmering
Spectrum is shown in Fig. 8, and carbon quantum dot fluorescence Spectra prepared by embodiment 2 is shown in Fig. 9, and carbon quantum dot fluorescence Spectra prepared by embodiment 3 is shown in Figure 10,
Carbon quantum dot fluorescence Spectra prepared by embodiment 4 is shown in Figure 11；From Fig. 8~11 it is found that fluorescence peak concentrates visible region.Embodiment 1
Strongest fluorescent emission is presented under the monochromatic light excitation that wavelength is 470nm in the carbon quantum dot of~4 preparations.
Embodiment 5
A kind of nitrogen, the sulphur of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method, the specific steps are as follows:
(1) it takes 2g glutaminol and 2g methionine to mill in agateware after mixing, is laid in beaker bottom,
Being subsequently placed on heating platform and being at the uniform velocity warming up to temperature is 250 DEG C, and is mixed in 250 DEG C of heated at constant temperature reaction 7min into beaker
Object carbonization, discoloration obtain reaction product；
(2) it is cooled to room temperature to the reaction product A in step (1), passivator (deionized water) is added to reaction product
In be uniformly mixed obtain mixed solution；
(3) the mixed solution B in step (2) heated at constant temperature 5min on the platform that temperature is 250 DEG C is again placed in obtain
Mixed solution C；
(4) centrifugal treating is carried out, is removed after standing through bag filter dialysis to room temperature after the mixed solution C in beaker is cooling
Unreacted raw material and other little particle impurity are removed, obtains nitrogen, sulphur is co-doped with carbon quantum dot；Wherein the revolving speed of centrifugal treating is
12000r/min, the time of centrifugal treating are 20min；The volume ratio of passivator (deionized water) and reaction product C are 20:1；Thoroughly
The molecule interception for analysing bag is 200k Da.
Embodiment 6
A kind of nitrogen, the sulphur of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method, the specific steps are as follows:
(1) it takes 4g glutaminol and 4g methionine to mill in agateware after mixing, is laid in beaker bottom,
Being subsequently placed on heating platform and being at the uniform velocity warming up to temperature is 250 DEG C, and is mixed in 250 DEG C of heated at constant temperature reaction 9min into beaker
Object carbonization, discoloration obtain reaction product；
(2) passivator (ethyl alcohol) is added in reaction product and is mixed but to room temperature to the cold A of reaction product in step (1)
It closes and uniformly obtains mixed solution；
(3) the mixed solution B in step (2) heated at constant temperature 5min on the platform that temperature is 250 DEG C is again placed in obtain
Mixed solution C；
(4) centrifugal treating is carried out, is removed after standing through bag filter dialysis to room temperature after the mixed solution C in beaker is cooling
Unreacted raw material and other little particle impurity are removed, obtains nitrogen, sulphur is co-doped with carbon quantum dot；Wherein the revolving speed of centrifugal treating is
12000r/min, the time of centrifugal treating are 20min；The volume ratio of passivator (ethyl alcohol) and reaction product C are 20:1；Bag filter
Molecule interception be 200k Da.
Embodiment 7
A kind of nitrogen, the sulphur of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method, the specific steps are as follows:
(1) it takes 6g glutaminol and 6g methionine to mill in agateware after mixing, is laid in beaker bottom,
Being subsequently placed on heating platform and being at the uniform velocity warming up to temperature is 300 DEG C, and is mixed in 300 DEG C of heated at constant temperature reaction 12min into beaker
Close object carbonization, discoloration obtains reaction product；
(2) it is cooled to room temperature to the reaction product A in step (1), passivator (deionized water) is added to reaction product
In be uniformly mixed obtain mixed solution；
(3) the mixed solution B in step (2) heated at constant temperature 6min on the platform that temperature is 300 DEG C is again placed in obtain
Mixed solution C；
(4) centrifugal treating is carried out, is removed after standing through bag filter dialysis to room temperature after the mixed solution C in beaker is cooling
Unreacted raw material and other little particle impurity are removed, obtains nitrogen, sulphur is co-doped with carbon quantum dot；Wherein the revolving speed of centrifugal treating is
12000r/min, the time of centrifugal treating are 20min；The volume ratio of passivator (deionized water) and reaction product C are 20:1；Thoroughly
The molecule interception for analysing bag is 300k Da.
Embodiment 8
A kind of nitrogen, the sulphur of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method, the specific steps are as follows:
(1) it takes 8g glutaminol and 8g methionine to mill in agateware after mixing, is laid in beaker bottom,
Being subsequently placed on heating platform and being at the uniform velocity warming up to temperature is 300 DEG C, and is mixed in 300 DEG C of heated at constant temperature reaction 15min into beaker
Close object carbonization, discoloration obtains reaction product；
(2) it is cooled to room temperature to the reaction product A in step (1), passivator (ethyl alcohol) is added in reaction product and is mixed
It closes and uniformly obtains mixed solution；
(3) the mixed solution B in step (2) heated at constant temperature 5min on the platform that temperature is 300 DEG C is again placed in obtain
Mixed solution C；
(4) centrifugal treating is carried out, is removed after standing through bag filter dialysis to room temperature after the mixed solution C in beaker is cooling
Unreacted raw material and other little particle impurity are removed, obtains nitrogen, sulphur is co-doped with carbon quantum dot；Wherein the revolving speed of centrifugal treating is
12000r/min, the time of centrifugal treating are 20min；The volume ratio of passivator (ethyl alcohol) and reaction product C are 20:1；Bag filter
Molecule interception be 300k Da.
Embodiment 9
A kind of nitrogen, the sulphur of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method, the specific steps are as follows:
(1) it takes 10g glutaminol and 10g methionine to mill in agateware after mixing, is laid in bottom of the beaker
Portion, being subsequently placed on heating platform and being at the uniform velocity warming up to temperature is 300 DEG C, and in 300 DEG C of heated at constant temperature reaction 20min into beaker
Mixture carbonization, discoloration obtain reaction product；
(2) it is cooled to room temperature to the reaction product A in step (1), passivator (deionized water) is added to reaction product
In be uniformly mixed obtain mixed solution；
(3) the mixed solution B in step (2) heated at constant temperature 8min on the platform that temperature is 300 DEG C is again placed in obtain
Mixed solution C；
(4) centrifugal treating is carried out, is removed after standing through bag filter dialysis to room temperature after the mixed solution C in beaker is cooling
Unreacted raw material and other little particle impurity are removed, obtains nitrogen, sulphur is co-doped with carbon quantum dot；Wherein the revolving speed of centrifugal treating is
12000r/min, the time of centrifugal treating are 20min；The volume ratio of passivator (deionized water) and reaction product C are 20:1；Thoroughly
The molecule interception for analysing bag is 300k Da；
Embodiment 5~9 prepare carbon quantum dot uv-visible absorption spectra it is as shown in figure 12, carbon quantum dot it is ultraviolet-
Visible absorption spectra absorption peak is focused on the UV light region 200~400nm；Carbon quantum dot fluorescence Spectra prepared by embodiment 5 is shown in
Figure 13, carbon quantum dot fluorescence Spectra prepared by embodiment 6 are shown in Figure 14, and carbon quantum dot fluorescence Spectra prepared by embodiment 7 is shown in Figure 15；Implement
Carbon quantum dot fluorescence Spectra prepared by example 8 is shown in Figure 16；Carbon quantum dot fluorescence Spectra prepared by embodiment 9 is shown in Figure 17.It can from Figure 13~17
Know, the fluorescence peak of carbon quantum dot is focused on visible light wave range.Carbon quantum dot prepared by example 5 is in the monochrome that wavelength is 510nm
Light excitation is lower to be presented strongest fluorescent emission；Carbon quantum dot prepared by example 6 is presented under the monochromatic light excitation that wavelength is 530nm
Strongest fluorescent emission；Strongest fluorescence hair is presented under the monochromatic light excitation that wavelength is 590nm in carbon quantum dot prepared by example 7
It penetrates；Strongest fluorescent emission is presented under the monochromatic light excitation that wavelength is 580nm in carbon quantum dot prepared by example 8,9；
From Fig. 8~11,13~17 it is found that carbon quantum dot most hyperfluorescence transmitting peak position prepared by example 1~9 is respectively as follows:
541nm, 547nm, 543nm, 538nm, 571nm, 586nm, 624nm, 635nm, 642nm, fluorescence emission wavelengths can be from green Regions
It is adjusted to red light district；
The chromatic diagram of carbon quantum dot prepared by Examples 1 to 9 is shown in Figure 18, and as can be seen from Figure 18, Water-soluble carbon quantum dot is
Typical luminescence generated by light fluorescent carbon quantum dot, wavelength of fluorescence can be adjusted to red light district from green Region；
Table 1 is the technological parameter table of comparisons of the carbon quantum dot of Examples 1 to 9 preparation；
Table 1
As it can be seen from table 1 being allowed to by changing preparation condition or passivator, that is, controllable carbon quantum dot wavelength of fluorescence
Cover green light, yellow light and red spectral band.
Claims (6)
1. a kind of nitrogen, the sulphur of adjustable wavelength of fluorescence are co-doped with carbon quantum dot preparation method, which is characterized in that specific step is as follows:
(1) glutaminol and methionine are milled after mixing, is laid in reaction container bottom, is then at the uniform velocity warming up to
200~300 DEG C, and react 5~20min in heated at constant temperature and obtain reaction product A；
(2) step (1) reaction product A is cooled to room temperature, passivator is added in reaction product A and is mixed
Solution B；
(3) the mixed solution B in step (2) 2~10min of heating reaction under the conditions of temperature is 200~300 DEG C is placed in again to obtain
Mixed solution C；
(4) mixed solution C of step (3) is cooled to room temperature, carries out centrifugal treating, is removed after standing through bag filter dialysis not anti-
The raw material and impurity answered obtain nitrogen, sulphur is co-doped with carbon quantum dot.
2. nitrogen, the sulphur of adjustable wavelength of fluorescence according to claim 1 are co-doped with carbon quantum dot preparation method, it is characterised in that:
The ratio of glutaminol and methionine is (1~3): (1~3) in step (1).
3. nitrogen, the sulphur of adjustable wavelength of fluorescence according to claim 1 are co-doped with carbon quantum dot preparation method, it is characterised in that:
Step (2) passivator is ethyl alcohol, deionized water, oxalic acid solution or sodium hydroxide solution.
4. nitrogen, the sulphur of adjustable wavelength of fluorescence according to claim 3 are co-doped with carbon quantum dot preparation method, it is characterized in that ethyl alcohol
Pure to analyze, the concentration of oxalic acid solution is 3~10g/L, and the concentration of sodium hydroxide solution is 3~10g/L.
5. nitrogen, the sulphur of adjustable wavelength of fluorescence according to claim 1 are co-doped with carbon quantum dot preparation method, it is characterised in that:
The volume ratio of step (2) passivator and reaction product A are (10~20): 1.
6. nitrogen, the sulphur of adjustable wavelength of fluorescence according to claim 1 are co-doped with carbon quantum dot preparation method, it is characterised in that:
The molecule interception of step (4) bag filter is 100~300k Da.
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