CN109337681A - A kind of preparation method and application of sulfur and nitrogen co-doped carbon quantum dot - Google Patents
A kind of preparation method and application of sulfur and nitrogen co-doped carbon quantum dot Download PDFInfo
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- CN109337681A CN109337681A CN201811398267.5A CN201811398267A CN109337681A CN 109337681 A CN109337681 A CN 109337681A CN 201811398267 A CN201811398267 A CN 201811398267A CN 109337681 A CN109337681 A CN 109337681A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 25
- 239000011593 sulfur Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 45
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 34
- 238000006396 nitration reaction Methods 0.000 claims abstract description 26
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 16
- 238000000502 dialysis Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 abstract description 13
- 230000003287 optical effect Effects 0.000 abstract description 12
- 230000000670 limiting effect Effects 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000010606 normalization Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- WZHKCFDUDKJGBA-UHFFFAOYSA-N N1CCNCC1.S1C=CC=C1 Chemical compound N1CCNCC1.S1C=CC=C1 WZHKCFDUDKJGBA-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000002525 ultrasonication Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Classifications
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Luminescent Compositions (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
The present invention provides a kind of preparation methods of sulfur and nitrogen co-doped carbon quantum dot, comprising the following steps: mixes phenthazine, sodium nitrite, methylene chloride and acetic acid, nitration reaction occurs, obtains 3,7- dinitro phenthazine；3, the 7- dinitro phenthazine and lye are mixed, hydro-thermal reaction is successively carried out, dialyses, obtains sulfur and nitrogen co-doped carbon quantum dot.Nitrogen source and sulphur source are nitrified the nitrogen content that can increase carbon quantum dot by the present invention first, then mix obtained 3,7- dinitro phenthazine and lye, and hydro-thermal reaction occurs, the carbon quantum dot of sulphur N doping is prepared.The content of nitrogen is 3.45wt%~9.69wt% in the carbon quantum dot, and the content of sulphur is 0.51wt%~0.83wt%, shows very strong nonlinear scattering performance, has extraordinary optical limiting properties.
Description
Technical field
The present invention relates to laser protective material technical fields, more particularly to a kind of sulfur and nitrogen co-doped carbon quantum dot and its system
Preparation Method and application.
Background technique
Carbon quantum dot is a kind of dispersion, size the fluorescence carbon nano-particle spherical in 10nm or less.With other fluorescence
Nanoparticle is compared, and carbon quantum dot also has other than having many advantages, such as that good biocompatibility and surface are easy to functionalization
There are many excellent optical physics feature: the dependence of excitation wavelength, photostability, pH value dependence, electrochemical luminescence, ultraviolet
There is strong absorption in area, has up-conversion fluorescence property.Above-mentioned excellent property passes carbon quantum dot in biological detection, biology
The fields such as sense, fluorescence probe, field of medicaments, photocatalysis are by important application value.
In recent years, people had started the research of the optical limiting properties for carbon quantum dot, but how can be prepared into
To a kind of sulfur and nitrogen co-doped carbon quantum dot of excellent optical limiting properties, there are no relevant reports in the prior art.
Summary of the invention
The purpose of the present invention is to provide a kind of sulfur and nitrogen co-doped carbon quantum dots with excellent optical limiting properties.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of sulfur and nitrogen co-doped carbon quantum dot, comprising the following steps:
Phenthazine, sodium nitrite, methylene chloride and acetic acid are mixed, nitration reaction occurs, obtains 3,7- dinitro pheno thiophene
Piperazine；
3, the 7- dinitro phenthazine and lye are mixed, hydro-thermal reaction is successively carried out, dialyses, obtains sulfur and nitrogen co-doped
Carbon quantum dot.
Preferably, the molar ratio of the phenthazine and sodium nitrite is 1:(5.5~6.5).
Preferably, the amount of the substance of the phenthazine and the volume ratio of methylene chloride be (0.08~0.12) mol:(180~
220)mL。
Preferably, the amount of the substance of the sodium nitrite and the volume ratio of acetic acid are (0.28~0.32) mol:(70~90)
mL。
Preferably, the temperature of the nitration reaction is 20~50 DEG C, and the time of the nitration reaction is 2~6h.
Preferably, the lye is the sodium hydrate aqueous solution of 0.2mol/L or the ammonium hydroxide of 1mol/L.
Preferably, the quality of 3, the 7- dinitro phenthazine and the volume ratio of lye are 1g:(180~220) mL.
Preferably, the temperature of the hydro-thermal reaction is 120~200 DEG C, and the time of the hydro-thermal reaction is 10~14h.
Preferably, the molecular cut off of the dialysis bag filter is 500~1000.
The present invention also provides application of the above-mentioned sulfur and nitrogen co-doped carbon quantum dot in lasing safety.
The present invention provides a kind of preparation methods of sulfur and nitrogen co-doped carbon quantum dot, comprising the following steps: by phenthazine,
Sodium nitrite, methylene chloride and acetic acid mixing, occur nitration reaction, obtain 3,7- dinitro phenthazine；By the 3,7- dinitro
Base phenthazine and lye mixing, successively carry out hydro-thermal reaction, dialyse, obtain sulfur and nitrogen co-doped carbon quantum dot.The present invention is first
Nitrogen source and sulphur source, which are carried out nitrification, can increase nitrogen content in carbon quantum dot, then by obtained 3,7- dinitro phenthazine and
Lye mixing, occurs hydro-thermal reaction, the carbon quantum dot of sulphur N doping is prepared.The content of nitrogen is in the carbon quantum dot
The content of 3.45wt%~9.69wt%, sulphur are 0.51wt%~0.83wt%, show very strong nonlinear scattering performance,
With extraordinary optical limiting properties.
Detailed description of the invention
Fig. 1 is the xps energy spectrum figure of the D-1 that embodiment 1 is prepared and the D-2 that embodiment 2 is prepared；
Fig. 2 is normalization luminous intensity figure of the D-1 that is prepared of embodiment 1 under different ionic strength；
Fig. 3 is normalization luminous intensity figure of the D-1 that is prepared of embodiment 1 under ultraviolet light irradiation different time；
Fig. 4 is the Z scanning figure of the D-1 that embodiment 1 is prepared and the D-2 that embodiment 2 is prepared；
Fig. 5 is the nonlinear scattering curve graph of the D-1 that embodiment 1 is prepared and the D-2 that embodiment 2 is prepared；
Fig. 6 is the optical limiting properties figure of the D-1 that embodiment 1 is prepared and the D-2 that embodiment 2 is prepared；
Fig. 7 is normalization luminous intensity figure of the D-2 that is prepared of embodiment 2 under different ionic strength；
Fig. 8 is normalization luminous intensity figure of the D-2 that is prepared of embodiment 2 under ultraviolet light irradiation different time.
Specific embodiment
The present invention provides a kind of preparation methods of sulfur and nitrogen co-doped carbon quantum dot, comprising the following steps:
Phenthazine, sodium nitrite, methylene chloride and acetic acid are mixed, nitration reaction occurs, obtains 3,7- dinitro pheno thiophene
Piperazine；
3, the 7- dinitro phenthazine and lye are mixed, hydro-thermal reaction is successively carried out, dialyses, obtains sulfur and nitrogen co-doped
Carbon quantum dot.
In the present invention, if without specified otherwise, all raw material components are commercial product well known to those skilled in the art.
The present invention mixes phenthazine, sodium nitrite, methylene chloride and acetic acid, and nitration reaction occurs, obtains 3,7- dinitro
Base phenthazine.In the present invention, the phenthazine is used as nitrogen source and sulphur source simultaneously；The sodium nitrite is nitrogen source；The dichloro
Methane is the solvent of phenthazine；The acetic acid is the solvent of sodium nitrite.
In the present invention, the molar ratio of the phenthazine and sodium nitrite is preferably 1:(5.5~6.5), more preferably 1:
(5.8~6.2).In the present invention, the amount of the substance of the phenthazine and the volume ratio of methylene chloride be preferably (0.08~
0.12) mol:(180~220) mL, more preferably (0.09~0.11) mol:(190~210) mL.In the present invention, the Asia
The amount of the substance of sodium nitrate and the volume ratio of acetic acid are preferably (0.28~0.32) mol:(70~90) mL, more preferably (0.29
~0.31) mol:(75~85) mL.
In the present invention, the temperature of the nitration reaction is preferably 20~50 DEG C, and more preferably 30~40 DEG C, most preferably
34~36 DEG C；The time of the nitration reaction is preferably 2~6h, more preferably 2.5~5h, most preferably 3~4h.
In the present invention, the nitration reaction preferably carries out under stirring conditions；Condition of the present invention to the stirring
There is no any special restriction, is carried out using stirring condition known to those skilled in the art technical staff.
In the present invention, the detailed process of the nitration reaction is preferred are as follows:
Under stirring conditions, 50% sodium nitrite is slowly added to the methylene chloride and 50% of phenthazine, 50%
Acetic acid mixture in, occur nitration reaction I；
Continue in above-mentioned reaction system be added 50% methylene chloride, 50% acetic acid and 50% sodium nitrite, hair
Raw nitration reaction II.
In the present invention, the time of the nitration reaction I and the time of nitration reaction II are than being preferably (0.5~1.5) h:
(1~3) h, more preferably (0.6~1.4) h:(1.4~2.6) h, most preferably (0.8~1.2) h:(1.6~2.4) h.
In the present invention, the nitration reaction substep carries out that the nitration reaction on phenthazine 3,7 can be promoted more abundant.
After the completion of nitration reaction, the present invention preferably post-processes the product system that nitration reaction obtains, and obtains 3,7-
Dinitro phenthazine；In the present invention, the post-processing preferably includes:
The product system that nitration reaction is obtained is mixed with acetic acid solution, is successively filtered, is washed, obtains crude product；
At 100 DEG C, the crude product is mixed with DMF, is filtered while hot, washed, it is dry, obtain 3,7- dinitro pheno thiophene
Piperazine.
The product system that the present invention obtains nitration reaction is mixed with acetic acid solution, is successively filtered, is washed, and is obtained thick
Product.In the present invention, the mass concentration of the acetic acid solution is preferably 90%~100%, and more preferably 95%~98%；It is described
The volume ratio of methylene chloride and acetic acid total volume and acetic acid solution is preferably 3:(1.5~5), more preferably 3:(2~4).At this
In invention, the effect of the acetic acid solution is the further Asia for removing and being not engaged in reaction in the product system that nitration reaction obtains
Sodium nitrate.
In the present invention, the mixing preferably carries out under stirring conditions；In the present invention, the time of the stirring is excellent
It is selected as 1.5~2.5h, more preferably 1.8~2.2h；The present invention does not have any special restriction to the rate of the stirring, uses
Stirring rate well known to those skilled in the art is stirred.
The present invention filters no any special restriction to described, using suction filtration process well known to those skilled in the art into
Row filters.
In the present invention, the washing preferably successively uses ethyl alcohol and water washing three times.
After obtaining crude product, the present invention is mixed at 100 DEG C, by the crude product with DMF, is filtered while hot, is washed, dry, is obtained
To 3,7- dinitro phenthazine.The present invention does not have any special restriction to the dosage of the DMF, using those skilled in the art
Well known dosage；In the present invention, the effect of the DMF is that further remove does not have in the product system that nitration reaction obtains
There is the phenthazine for participating in reacting.
The present invention to the no any special restriction of the filtering, using filter condition well known to those skilled in the art into
Row.
In the present invention, the washing is preferably ethyl alcohol with detergent；The present invention does not have the detailed process of the washing
Any special restriction, is washed using washing process well known to those skilled in the art.
The present invention any special restriction no to the drying, using drying process well known to those skilled in the art into
Row is dry.
After obtaining 3,7- dinitro phenthazine, the present invention mixes 3, the 7- dinitro phenthazine and lye, successively into
Row hydro-thermal reaction and dialysis obtain sulfur and nitrogen co-doped carbon quantum dot.In the present invention, the lye is preferably 0.2mol/L's
The ammonium hydroxide of sodium hydrate aqueous solution or 1mol/L.In the present invention, the body of the quality of 3, the 7- dinitro phenthazine and lye
Product is than being preferably 1g:(180~220) mL, more preferably 1g:(190~210) mL.In the present invention, the mixed time is excellent
It is selected as 1.5~2.5h, more preferably 1.8~2.2h.In the present invention, the mixing preferably carries out under conditions of ultrasound；This
Invention does not have any special restriction to the rate of the ultrasound, is using ultrasonic rate well known to those skilled in the art
It can.
In the present invention, the temperature of the hydro-thermal reaction is preferably 120~200 DEG C, more preferably 140~180 DEG C, optimal
It is selected as 160~170 DEG C；The time of the hydro-thermal reaction is preferably 10~14h, more preferably 12~13h.
In the present invention, after the completion of the hydro-thermal reaction, preferably obtained product system is successively cooled down and is filtered；
In the present invention, the cooling is preferably cooled to room temperature；In the present invention, the filtering preferably leads to product system
The filter membrane that aperture is 0.22 micron is crossed, to remove the responseless raw material of bulky grain carbon material not soluble in water and part.
In the present invention, the molecular cut off of the bag filter of the dialysis is preferably 500~1000, and more preferably 600
~800.
In the present invention, the purpose of the dialysis is the small molecule for removing sodium salt and not being carbonized.
After the completion of dialysis, the present invention is preferably dried the solid matter obtained after dialysis；In the present invention, described dry
It is dry to be preferably dried in vacuo；The vacuum drying temperature is preferably 40~60 DEG C, and more preferably 45~55 DEG C；The vacuum is dry
The dry time is preferably 20~30h, more preferably 22~28h, most preferably 24~26h.
The present invention also provides the sulfur and nitrogen co-doped carbon quantum dot that above-mentioned preparation method is prepared, the sulphur nitrogen is co-doped with
The content of nitrogen is 3.45wt%~9.69wt% in miscellaneous carbon quantum dot, and the content of sulphur is 0.51wt%~0.83wt%.
The present invention also provides application of the above-mentioned sulfur and nitrogen co-doped carbon quantum dot in lasing safety.
Below with reference to embodiment to the carbon quantum dot and its preparation method and application of the sulphur N doping provided by the invention
It is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The synthesis of 3,7- dinitro phenthazine:
Under stirring conditions, in the mixing of 20.00g phenthazine (100mmol), 100mL methylene chloride and 40mL acetic acid
In object, it is slowly added to 20.00g sodium nitrite (300mmol), after 1h is stirred at room temperature, adds 100mL methylene chloride, 40mL second
Acid and 20.00g sodium nitrite react 1.5h, have a large amount of solids to generate；120mL acetic acid dilute solution is added to system again, continues
It is filtered after stirring 2h, three times with ethyl alcohol and water washing.Then obtained solid is dissolved in 100 DEG C of DMF, is filtered while hot, filter cake
3, the 7- dinitro phenthazine (yield 86%) of aubergine is obtained with drying after ethanol washing filter cake for product.1HNMR
(400MHz；DMSO-d6): 6.69 (d, J=4Hz, 2H), 7.70 (s, 2H), 7.82 (d, J=4Hz, 2H).HRMS(ESI)m/z
C12H8N3O4S+(M+H)+Calculated value: 290.0230, measured value: 290.0245.Elemental analysis calculated value: C, 49.83；H,2.44；
N,14.53；Measured value: C, 49.95；H,2.51；N,14.61.
The synthesis of sulfur and nitrogen co-doped carbon quantum dot:
Under conditions of ultrasound, 3,7- dinitro phenthazine (0.3g) is dispersed in the sodium hydroxide of the 0.2mol/L of 60mL
In aqueous solution, ultrasound 2h is kept, suspension is obtained, at 200 DEG C, reacts 12h.It is cooled to room temperature after the reaction was completed, uses aperture
For 0.22 micron of membrane filtration reaction solution, the bulky grain responseless raw material of carbon material and part not soluble in water is removed.It will
It is dialysed after filtrate concentration with the bag filter that molecular cut off is 500~1000, the small molecule for removing sodium salt and not being carbonized,
Vacuum drying, obtains the carbon quantum dot of sulphur N doping, is denoted as D-1.D-1 is almost spherical, the distribution of partial size is 1.5~
4.5nm, average grain diameter 2.8nm；
Fig. 2 is normalization luminous intensity figure of the D-1 under different ionic strength, as seen from the figure, the fluorescence of the quantum dot
Emissive porwer will not decline with the increase of solution ion strength, have good resistance to ionic strength performance；
Fig. 3 is the normalization luminous intensity figure of D-1 under conditions of ultraviolet light irradiation different time, as seen from the figure, with
The increase of irradiation time, fluorescence intensity are only declined slightly, and show outstanding photostability.
Embodiment 2
The synthesized reference embodiment 1 of 3,7- dinitro phenthazine；
The synthesis of sulfur and nitrogen co-doped carbon quantum dot:
Under conditions of ultrasound, by the ammonia spirit of 0.3g 3,7- dinitro the phenthazine 1mol/L for being dispersed in 60mL,
2h is kept, suspension is obtained, at 200 DEG C, reacts 12h.It is cooled to room temperature after the reaction was completed, the filter for being 0.22 micron with aperture
Film filtering reacting liquid removes the bulky grain responseless raw material of carbon material and part not soluble in water.It uses and cuts after filtrate is concentrated
Staying molecular weight is that the bag filter of 500-1000 is dialysed, and the small molecule for removing sodium salt and not being carbonized, vacuum drying obtains sulphur
The carbon quantum dot of N doping, is denoted as D-2.The pattern of D-2 is almost spherical, and the distribution of partial size is 1.5~4nm, average grain
Diameter is 3.1nm；
Fig. 7 is normalization luminous intensity figure of the D-2 under different ionic strength, as seen from the figure, the fluorescence of the quantum dot
Emissive porwer will not decline with the increase of solution ion strength, have good resistance to ionic strength performance；
Fig. 8 is the normalization luminous intensity figure of D-2 under conditions of ultraviolet light irradiation different time, as seen from the figure, with
The increase of irradiation time, fluorescence intensity are only declined slightly, and show outstanding photostability；
Fig. 1 is the xps energy spectrum figure of D-1 and D-2, and as seen from the figure, D-1 is mainly made of tetra- kinds of elements of C, O, N and S, is passed through
Calculating four kinds of element wt ratios is C:O:N:S=55.34%:36.15%:3.45%:0.83%, and wherein nitrogen is former with pyridine state nitrogen
The form of son, amino nitrogen atom and pyrroles's state nitrogen-atoms exists；Sulphur is mainly with S2P3/2C-S-C and S2P1/2C-S-C form
In the presence of；D-2 is mainly made of tetra- kinds of elements of C, O, N and S, is C:O:N:S=58.59% by calculating four kinds of element wt ratios:
26.39%:9.69%:0.51%, wherein nitrogen is deposited in the form of pyridine state nitrogen-atoms, amino nitrogen atom and pyrroles's state nitrogen-atoms
?；Sulphur is mainly with S2P3/2C-S-C and S2P1/2C-S-C form exist；
Fig. 4 is the Z scanning figure of D-1 and D-2, as seen from the figure, strong through the light beam of sample as sample distance focal point is closer
Degree increases, and optical limitation increases, and in DMF solution, the ultrasonication that D-1 carries out 30min in DMF is dispersed, and
It is 70% that transmitance is kept at 532nm.Under the 532nm laser of 4ns pulse, when sample is close to during focus, because focusing
Laser energy is maximum at point, and the transmitance of D-1 gradually decreases and drops to 72%, D-2 in focal point carries out 30min in DMF
Ultrasonication dispersion, and 532nm at keep transmitance be 70%.Under the 532nm laser of 4ns pulse, when sample connects
During perifocus, because focal spot laser energy is maximum, the transmitance of D-1 gradually decreases and drops in focal point
64%；
Fig. 5 is the nonlinear scattering curve graph of D-1 and D-2, and as seen from the figure, D-1 and D-2 show certain scattering and ring
It answers, can be used as good nonlinear scattering body and effective optical limiting materials；
Fig. 6 is the optical limiting properties figure of D-1 and D-2, and as seen from the figure, under 532nm wavelength, D-1 and D-2 are all had very
Good optical limiting properties.
As seen from the above embodiment, the sulfur and nitrogen co-doped carbon quantum dot tool that preparation method of the present invention is prepared
There is extraordinary optical limitation.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of sulfur and nitrogen co-doped carbon quantum dot, comprising the following steps:
Phenthazine, sodium nitrite, methylene chloride and acetic acid are mixed, nitration reaction occurs, obtains 3,7- dinitro phenthazine；
3, the 7- dinitro phenthazine and lye are mixed, hydro-thermal reaction and dialysis is successively carried out, obtains sulfur and nitrogen co-doped
Carbon quantum dot.
2. preparation method as described in claim 1, which is characterized in that the molar ratio of the phenthazine and sodium nitrite is 1:
(5.5~6.5).
3. preparation method as described in claim 1, which is characterized in that the amount of the substance of the phenthazine and the body of methylene chloride
Product is than being (0.08~0.12) mol:(180~220) mL.
4. preparation method as described in claim 1, which is characterized in that the amount of the substance of the sodium nitrite and the volume of acetic acid
Than for (0.28~0.32) mol:(70~90) mL.
5. preparation method as described in claim 1, which is characterized in that the temperature of the nitration reaction is 20~50 DEG C, described
The time of nitration reaction is 2~6h.
6. preparation method as described in claim 1, which is characterized in that the lye is the sodium hydrate aqueous solution of 0.2mol/L
Or the ammonium hydroxide of 1mol/L.
7. preparation method as described in claim 1, which is characterized in that the quality of 3, the 7- dinitro phenthazine and lye
Volume ratio is 1g:(180~220) mL.
8. preparation method as described in claim 1, which is characterized in that the temperature of the hydro-thermal reaction is 120~200 DEG C, institute
The time for stating hydro-thermal reaction is 10~14h.
9. preparation method as described in claim 1, which is characterized in that the molecular cut off of the dialysis bag filter is 500
~1000.
10. the sulfur and nitrogen co-doped carbon quantum dot that preparation method according to any one of claims 1 to 9 is prepared is anti-in laser
Application in shield.
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| CN111603570A (en) * | 2020-07-06 | 2020-09-01 | 南京工业大学 | Carbon-point-modified hollow copolymer nano particle, preparation method and application thereof, drug delivery system and application thereof |
| CN113249122A (en) * | 2021-04-14 | 2021-08-13 | 复旦大学 | Photoinduced carbon quantum dot and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102718730A (en) * | 2006-07-11 | 2012-10-10 | 维斯塔实验室有限公司 | Methods of synthesis and/or purification of diaminophenothiazinium compounds |
| CN108675280A (en) * | 2018-06-21 | 2018-10-19 | 大连理工大学 | phenothiazine derivative fluorescent carbon point and its preparation method and application |
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2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102718730A (en) * | 2006-07-11 | 2012-10-10 | 维斯塔实验室有限公司 | Methods of synthesis and/or purification of diaminophenothiazinium compounds |
| CN108675280A (en) * | 2018-06-21 | 2018-10-19 | 大连理工大学 | phenothiazine derivative fluorescent carbon point and its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111603570A (en) * | 2020-07-06 | 2020-09-01 | 南京工业大学 | Carbon-point-modified hollow copolymer nano particle, preparation method and application thereof, drug delivery system and application thereof |
| CN111603570B (en) * | 2020-07-06 | 2021-04-30 | 南京工业大学 | Carbon-point-modified hollow copolymer nano particle, preparation method and application thereof, drug delivery system and application thereof |
| CN113249122A (en) * | 2021-04-14 | 2021-08-13 | 复旦大学 | Photoinduced carbon quantum dot and preparation method thereof |
| CN113249122B (en) * | 2021-04-14 | 2022-04-12 | 复旦大学 | Photoinduced carbon quantum dot and preparation method thereof |
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