CN116948639A - Carbon dot/dye@metal organic framework composite material and preparation method and application thereof - Google Patents
Carbon dot/dye@metal organic framework composite material and preparation method and application thereof Download PDFInfo
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- CN116948639A CN116948639A CN202310863635.3A CN202310863635A CN116948639A CN 116948639 A CN116948639 A CN 116948639A CN 202310863635 A CN202310863635 A CN 202310863635A CN 116948639 A CN116948639 A CN 116948639A
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 239000000975 dye Substances 0.000 claims abstract description 42
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 7
- -1 mercury ions Chemical class 0.000 claims abstract description 7
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 claims description 38
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 21
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 21
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- CBMCZKMIOZYAHS-NSCUHMNNSA-N [(e)-prop-1-enyl]boronic acid Chemical compound C\C=C\B(O)O CBMCZKMIOZYAHS-NSCUHMNNSA-N 0.000 claims description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims description 2
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 claims description 2
- XJCPMUIIBDVFDM-UHFFFAOYSA-M nile blue A Chemical compound [Cl-].C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4[O+]=C3C=C(N)C2=C1 XJCPMUIIBDVFDM-UHFFFAOYSA-M 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000012984 biological imaging Methods 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 3
- 238000000862 absorption spectrum Methods 0.000 abstract description 2
- 238000000295 emission spectrum Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 86
- 239000000243 solution Substances 0.000 description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000013207 UiO-66 Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000012917 MOF crystal Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 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
- 238000010586 diagram Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 239000002351 wastewater Substances 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Abstract
The invention provides a carbon dot/dye@metal organic framework composite material, a preparation method and application thereof, wherein CDs and dye obtained by preparation are added in the synthesis process of a metal organic framework, so that the CDs/dye@metal organic framework composite material is prepared, has a relatively wide absorption spectrum and emission spectrum, and can change the types of CDs and dye according to requirements so as to change the positions of double (multiple) fluorescence emission peaks, and the synthesis method is simple and convenient. The fluorescent composite material has high stability of a metal organic framework and tunable excitation wavelength of CDs, has been successfully used for establishing a ratio fluorescent probe to detect mercury ions, and is also expected to be applied to photocatalysis, anti-counterfeiting materials, biological imaging, pollutant degradation, LED luminescent materials and other aspects.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a carbon dot/dye@metal organic framework composite material, and a preparation method and application thereof.
Background
The carbon quantum dot has the advantages of excellent optical property, good water solubility, low toxicity, environmental friendliness, wide raw material source, low cost, good biocompatibility and the like. Since the first discovery of carbon quantum dots, many synthetic methods have been developed, including arc discharge, laser pinning, electrochemical synthesis, chemical oxidation, combustion, hydrothermal synthesis, microwave synthesis, template, and the like.
The carbon dot CDs have excellent performances of high photo-thermal stability, easy surface modification, adjustable composition, fluorescence emission, good biocompatibility, low cytotoxicity and the like, so that the carbon dot CDs are promising nano materials in the aspects of fluorescent probes, chemical and biological sensing, drug detection, drug transfer, photocatalysis and the like. Most CDs reported at present are single fluorescence peaks of blue luminescence, and are easily interfered by other substances and uncontrollable factors such as instrument voltage and concentration change.
The metal organic framework is used as a novel porous material composed of organic ligands and metal ions, has various excellent characteristics such as an adjustable framework structure, a large specific surface area, an adjustable aperture, an adjustable shape and the like, and the highly porous structure of the metal organic framework can be used for developing nano-cluster/metal organic framework composite materials so as to enhance the fluorescence performance of the nano-clusters.
However, currently there is less research into dual (poly) emission fluorescent materials.
Disclosure of Invention
The invention aims to provide a carbon dot/dye@metal-organic framework composite material and a preparation method thereof, CDs with blue fluorescence and dye with high quantum yield are embedded into a metal-organic framework, and a novel metal-organic framework with double-emission fluorescence peaks is developed, which shows excellent water solubility and double-emission fluorescence peaks, not only avoids fluorescence quenching caused by aggregation induction of CDs and dye molecules, but also can maintain stability and photochemical activity of CDs and dye.
It is also an object of the present invention to provide the use of carbon dot/dye @ metal organic framework composites for the detection of mercury ions with ratiometric fluorescent probes.
The specific technical scheme of the invention is as follows:
a preparation method of a carbon dot/dye@metal organic framework composite material specifically comprises the following steps:
in the preparation process of the metal organic framework, CDs and dye are added, stirred and mixed uniformly, and reacted to obtain the metal organic framework.
The metal-organic framework is selected from ZIF-8, uiO-66 or ZIF-67;
such dyes include, but are not limited to, rhodamine 6G (Rh 6G), rhodamine B, nile blue, neutral red, fluorescein, or quinaldine red;
the CDs (carbon dots) are CDs with emission wavelength of 350-700 nm; the CDs are synthesized by a hydrothermal or microwave method;
after the reaction, the CDs/dye@metal organic framework composite material powder is obtained through washing, centrifuging and drying.
The CDs comprise, but are not limited to, carbon dots prepared by taking citric acid and urea or citric acid and ethylenediamine as raw materials;
preferably, the preparation method of the CDs comprises the following steps:
dissolving citric acid and urea in ultrapure water, stirring and dissolving by ultrasonic, transferring into a Teflon lining, heating the assembled reaction kettle in a baking oven with a set temperature, taking out the reaction liquid after the reaction is finished, and filtering, centrifuging and dialyzing to obtain CDs.
The carbon dot/dye@metal organic framework composite material is CDs/Rh6G@ZIF-8, CDs/Rh6G@UiO-66.
Preferably, the carbon dot/dye@metal organic framework composite material is CDs/Rh6G@ZIF-8, and the preparation method comprises the following steps: 2-methylimidazole and zinc nitrate are respectively dissolved in methanol, the obtained zinc nitrate solution is dripped into the 2-methylimidazole solution, CDs and rhodamine 6G are immediately added after the dripping is finished, then the mixture is continuously stirred and uniformly mixed, the mixture is kept stand for 12 to 36 hours, the reaction is finished, the obtained solid is washed and centrifuged for 3 to 5 times, and finally the obtained solid is dried to obtain CDs/Rh6G@ZIF-8 orange red powder.
The mass ratio of the 2-methylimidazole to the zinc nitrate is 1:1-10:1, preferably 2:1;
the concentration of the 2-methylimidazole in methanol is 0.01-0.05g/mL;
the mass ratio of the 2-methylimidazole to the CDs is 100:1-10; preferably 100:1, a step of;
the mass ratio of CDs to rhodamine 6G is 1:0.48-0.51, and preferably 1:0.5;
the growth of ZIF-8 is a surface limiting process, and the formation of ZIF-8 is affected by the amount of ligand or ion in the solvent. During the synthesis process, the reaction of 2-methylimidazole/Zn 2+ The ratio increases, larger particles of ZIF-8 are formed, and larger particles of ZIF-8 are formed by aggregation of smaller ZIF-8 nanocrystals. And 2-methylimidazole and Zn 2+ The ions can form ZIF-8 nuclei in a short time. Thus, 2-methylimidazole/Zn 2+ The ratio and the solvent volume of the catalyst have great influence on the appearance of ZIF-8, and the appearance of the products obtained by different addition amounts is different.
Preferably, the carbon dot/dye@metal organic framework composite material is CDs/Rh6G@UIO-66, and the preparation method comprises the following steps: respectively dissolving terephthalic acid and sodium acetate in N, N-dimethylformamide DMF, uniformly mixing the obtained two solutions by ultrasonic, adding zirconium tetrachloride, continuing ultrasonic until the zirconium tetrachloride is completely dissolved, then adding CDs and Rh6G into the solution, transferring the mixed liquid into a Teflon lining reaction kettle, heating for reaction, taking out the reaction liquid after the reaction is finished, and obtaining CDs/Rh6G@UiO-66 orange-red powder after centrifugal drying for a plurality of times.
The mass ratio of the terephthalic acid to the sodium acetate is 1:1-5:1, preferably 3:1;
the concentration of the terephthalic acid in DMF is 0.01-0.05g/mL;
the mass ratio of the terephthalic acid to the zirconium tetrachloride is 5-7:1, preferably 6:1;
the mass ratio of the zirconium tetrachloride to the CDs to the Rh6G is 1:0.04-0.06:0.025-0.035, preferably 1:0.05:0.025;
the heating reaction is that the reaction is carried out for 4+/-0.5 h at the temperature of 120+/-10 ℃;
the dye of the composite material is modified on the surface of the carbon quantum dot, the color of a product can be adjusted by adjusting the dosage, and then the carbon quantum dot modified with the dye is packed into a cavity of the MOF crystal in the MOF crystal forming process.
The carbon dot/dye@metal organic framework composite material provided by the invention is prepared by adopting the method.
The application of the carbon dot/dye@metal organic framework composite material provided by the invention is used for detecting heavy metal ions by a ratio fluorescent probe, and is preferably used for detecting mercury ions.
The invention develops a novel metal organic framework with double-emission fluorescence peaks by embedding CDs with blue fluorescence and dyes with high quantum yield into the metal organic framework. The dye is used for modifying and regulating the fluorescence emission and the color of the carbon quantum dots, and the carbon quantum dots are wrapped in the MOF, so that the effect achieved has the advantages of both the two, and experiments show that CDs/dye@metal organic frameworks show excellent water solubility and double-emission fluorescence peaks, so that fluorescence quenching caused by aggregation induction of CDs and dye molecules is avoided, and stability and photochemical activity of the CDs and the dye can be maintained. The synthesized CDs/dye@metal organic framework is expected to be applied to double emission peaks of a ratio fluorescent probe and a ratio fluorescent sensor, and a self-calibration system can be established by reference of the two peaks, so that the environmental influence is eliminated, and the sensitivity to target analytes is improved. It can also be used for photocatalysis, anti-counterfeiting materials, biological imaging, pollutant degradation and LED luminescent materials. The degraded pollutant includes antibiotics, organic dye, cosmetics, etc. the pollutant may be contained in natural water.
Compared with the prior art, the CDs/dye@metal organic framework composite material is prepared by adding the prepared CDs and dye in the synthesis process of the metal organic framework, has a relatively wide absorption spectrum and emission spectrum, and can change the types of the CDs and the dye according to requirements so as to change the positions of double (multiple) fluorescence emission peaks, and the synthesis method is simple and convenient. The fluorescent composite material has high stability of a metal organic framework and tunable excitation wavelength of CDs, has been successfully used for establishing a ratio fluorescent probe, and is expected to be applied to photocatalysis, anti-counterfeiting materials, biological imaging, pollutant degradation, LED luminescent materials and the like.
Drawings
FIG. 1 is a high resolution transmission electron microscope image of CDs prepared in example 1;
FIG. 2 is an ultraviolet-fluorescence spectrum of CDs prepared in example 1;
FIG. 3 is a scanning electron microscope image of ZIF-8 prepared in example 2;
FIG. 4 is a scanning electron microscope image of UiO-66 obtained in example 3;
FIG. 5 is a scanning electron microscope image of CDs/Rh6G@ZIF-8 prepared in example 4;
FIG. 6 is an infrared spectrum of CDs/Rh6G@ZIF-8 prepared in example 4;
FIG. 7 is an XRD spectrum of CDs/Rh6G@ZIF-8 prepared in example 4;
FIG. 8 is an ultraviolet-fluorescence spectrum of CDs/Rh6G@ZIF-8 prepared in example 4;
FIG. 9 shows the CDs/Rh6G@ZIF-8 obtained in example 4 and Hg at different concentrations 2+ Mixed fluorescence emission spectra;
FIG. 10 shows the CDs/Rh6G@ZIF-8 obtained in example 4 and Hg at different concentrations 2+ A mixed linear relationship;
FIG. 11 is a scanning electron microscope image of ZIF-8 prepared in example 6;
FIG. 12 is a scanning electron microscope image of CDs/Rh6G@ZIF-8 prepared in example 7;
FIG. 13 is a scanning electron microscope image of CDs/Rh6G@ZIF-8 prepared in example 8;
FIG. 14 is a schematic diagram of CDs/Rh6G@ZIF-8 synthesis of example 4.
Detailed Description
The following describes various exemplary embodiments of the invention and such detailed description should not be taken as limiting the invention, but rather as limiting the invention to specific embodiments, but rather as containing, but not limited to, the following examples, which are more detailed descriptions of the invention.
Although the invention has been described in terms of preferred methods and materials, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. Various modifications and alterations to this particular embodiment of this invention may be made without departing from the scope, spirit and spirit of this invention, as will be readily apparent to those skilled in the art.
Example 1
Preparation of CDs:
accurately weighing 0.5000g of citric acid and 0.3000g of urea in a 50mL beaker, adding 20mL of ultrapure water, ultrasonically dissolving, transferring into a Teflon lining, putting the assembled reaction kettle into an oven preheated to 160 ℃ in advance, and reacting for 10 hours. And after the reaction is finished, taking out the reaction kettle, cooling to room temperature, filtering the solution obtained by the reaction to remove large-particle impurities, then transferring the filtrate into a centrifuge tube, centrifuging to remove small-particle impurities, transferring the upper-layer solution obtained by the centrifugation into a dialysis bag for dialysis for 48 hours, and performing vacuum freeze-drying on CDs obtained by the dialysis to obtain black brown CDs powder.
Example 2
Preparation of ZIF-8:
0.6000g of 2-methylimidazole and 0.3000g of zinc nitrate are respectively dissolved in 20mL of methanol, the obtained zinc nitrate solution is dropwise added into the 2-methylimidazole solution under the stirring condition, the reaction is completed after the dropwise addition, the mixture is left stand for 24 hours, after the reaction is completed, the obtained solid is washed by methanol for 8000r/min and centrifuged for 5 times, and the solid is dried in vacuum at 60 ℃ to obtain ZIF-8 white powder.
Example 3
Preparation of UiO-66:
dissolving 0.4000g of terephthalic acid and 0.5000g of sodium acetate in 20mL of DMF respectively, uniformly mixing the obtained mixed fields by ultrasonic, adding 0.1000g of zirconium tetrachloride, continuing ultrasonic until the zirconium tetrachloride is completely dissolved, transferring the mixed liquid into a Teflon lining, placing the assembled reaction kettle into an oven with the set temperature of 120 ℃ for heating reaction for 4 hours, after the reaction, washing the obtained solid with methanol, centrifuging at 8000r/min for 5 times, and vacuum drying at 60 ℃ to obtain UIO-66 white powder.
Example 4
A preparation method of a carbon dot/dye@metal organic framework composite material specifically comprises the following steps:
0.6000g of 2-methylimidazole and 0.3000g of zinc nitrate are respectively dissolved in 20mL of methanol, the zinc nitrate solution is dropwise added into the 2-methylimidazole solution under stirring, 0.0060g of CDs prepared in example 1 and 0.0030g of Rh6G are immediately added after the dropwise addition, the total volume is regulated to be 50mL by adding methanol, the mixture is kept stand for 24 hours, and then is washed and centrifuged by methanol for 5 times at 8000r/min, and the mixture is dried in vacuum at 60 ℃ to obtain light reddish brown solid powder CDs/Rh6G@ZIF-8.
FIG. 5 is a scanning electron microscope image of CDs/Rh6G@ZIF-8 prepared in example 4; FIG. 6 is an infrared spectrum of CDs/Rh6G@ZIF-8 prepared in example 4; FIG. 7 is an XRD spectrum of CDs/Rh6G@ZIF-8 prepared in example 4; FIG. 8 is an ultraviolet-fluorescence spectrum of CDs/Rh6G@ZIF-8 prepared in example 4; the resulting product can be seen to have both carbon dots and fluorescence emission peaks of the dye, and XRD can also see that the complex has peaks of both MOF and CDs.
Example 5
A preparation method of a carbon dot/dye@metal organic framework composite material specifically comprises the following steps:
accurately weighing 0.6000g of terephthalic acid and 0.2000g of sodium acetate, dissolving in 20mL of DMF, carrying out ultrasonic treatment to dissolve the terephthalic acid and the sodium acetate, then adding 0.1000g of zirconium tetrachloride into the solution, continuing ultrasonic treatment for 10min until the zirconium tetrachloride is completely dissolved, adding 0.0050g of CDs prepared in example 1 and 0.0025g of Teflon 6G into the solution, transferring the reaction solution into a lining of Teflon, and placing the assembled reaction kettle in a baking oven at 120 ℃ for reaction for 4h. And after the reaction is finished, washing and centrifuging the solid obtained by the reaction with methanol, centrifuging for 5 times at 8000r/min, and drying the solid obtained by the centrifugation in a vacuum drying oven to obtain light red solid powder CDs/Rh6G@UiO-66.
Example 6
Preparation of ZIF-8:
0.70000 g of 2-methylimidazole and 0.2500g of zinc nitrate are respectively dissolved in 20mL of methanol, the zinc nitrate solution is dropwise added into the 2-methylimidazole solution under stirring, after the addition is completed, the solution is kept stand for 24 hours, washed and centrifuged for 5 times by using 8000r/min of methanol, and vacuum drying is carried out at 60 ℃ to obtain white solid powder ZIF-8.
Example 7 (as a comparison)
A preparation method of a carbon dot/dye@metal organic framework composite material specifically comprises the following steps:
0.6000g of 2-methylimidazole and 0.3000g of zinc nitrate were dissolved in 20mL of methanol, respectively, and the zinc nitrate solution was added dropwise to the 2-methylimidazole solution under stirring, and after the addition, 0.0060g of CDs prepared in example 1 was added,continuing Stirring for 10minSubsequently, 0.0030G of rhodamine 6G was added, methanol was added to adjust the total volume to be 50mL, and after standing for 24 hours, the mixture was centrifuged for 5 times by washing with methanol 8000r/min, and dried under vacuum at 60 ℃, to obtain pale reddish brown solid powder CDs/Rh6G@ZIF-8.
Example 8 (as a comparison)
A preparation method of a carbon dot/dye@metal organic framework composite material specifically comprises the following steps:
0.6000g of 2-methylimidazole and 0.3000g of zinc nitrate are respectively dissolved in 20mL of methanol, the zinc nitrate solution is dropwise added into the 2-methylimidazole solution under the stirring condition,stirring the mixture for 10 minutes,then 0.0060g of CDs prepared in example 1 were added,stirring for 10minAdding 0.0030G of rhodamine 6G, adding methanol to adjust the total volume to be 50mL, standing for 24 hours, washing and centrifuging for 5 times by using the methanol of 8000r/min, and vacuum drying at 60 ℃ to obtain light reddish brown solid powder CDs/Rh6G@ZIF-8.
As can be seen by comparing examples 4, 7 and 8, the addition of CDs and rhodamine 6G at different times has a great effect on the morphology of the resulting CDs/Rh6G@ZIF-8. Example 4 in the initial stage of ZIF-8 formation, CDs and rhodamine 6G were added to further favor the formation of ZIF-8 coated CDs and rhodamine 6G. In contrast, examples 7 and 8, CDs or rhodamine 6G was added after ZIF-8 was synthesized for 10min, which resulted in the formation of large and extremely irregular CDs/Rh6G@ZIF-8 (FIGS. 12 and 13). This may be CDs or rhodamine 6G having functional groups similar to anionic surfactants that act as bridges between the small ZIF-8 particles formed at the beginning of the reaction, which results in cross-linking between the small ZIF-8 particles formed, ultimately forming a very bulky and highly irregular "cross-linked" product of the three CDs, rh6G and ZIF-8. Therefore, when synthesizing the metal organic framework material, carbon dots and dye are added in the initial stage of crystal formation, which is favorable for forming regular morphology, otherwise irregular compound can be obtained.
Example 9
Preparing the CDs/Rh6G@ZIF-8 aqueous solution prepared in example 4, wherein the concentration is controlled to control the maximum intensity of a carbon dot fluorescence peak to 8000; taking the CDs/Rh6G@ZIF-8 solution with the same concentration and the same volume as Hg with different concentrations 2+ The solutions were mixed homogeneously and diluted to the same volume with the same pH buffer, both 3mL, hg 2+ Final concentration 5×10 -7 mol/L、7.5×10 -7 mol/L、1×10 -6 mol/L、1.25×10 -6 mol/L、1.5×10 -6 mol/L, standing for 10min at room temperature, taking 360nm as excitation wavelength, and observing and recording each group of fluorescence emission spectra.
FIG. 9 shows the CDs/Rh6G@ZIF-8 obtained in example 4 and Hg at different concentrations 2+ Mixed fluorescence emission spectra; FIG. 10 shows the CDs/Rh6G@ZIF-8 obtained in example 4 and Hg at different concentrations 2+ A mixed linear relationship; the CDs/Rh6G@ZIF-8 prepared by the invention has the advantages that 2+ The detection has good linear relation, low detection limit and higher sensitivity.
Hg was simulated 2+ The polluted wastewater sample is detected, the recovery rate is calculated, and the result is shown in table 1.
TABLE 1 detection of Hg by CDs/Rh6G@ZIF-8 prepared in example 4 2+ Testing
The fluorescent composite material prepared from CDs, dyes and metal organic frameworks has a wider ultraviolet-visible absorption and fluorescence emission range, and can adjust double (multi) fluorescence emission peaks according to requirements. In addition, the composite material is also expected to be used in photocatalysis, anti-counterfeiting materials, pollutant degradation, LED luminescent materials and other aspects.
Claims (9)
1. The preparation method of the carbon dot/dye@metal organic framework composite material is characterized by comprising the following steps of:
in the preparation process of the metal organic framework, CDs and dye are added, stirred and mixed uniformly, and reacted to obtain the metal organic framework.
2. The method of claim 1, wherein the metal-organic framework is selected from the group consisting of ZIF-8, uo-66 and ZIF-67.
3. The method of preparation of claim 1, wherein the dye includes, but is not limited to, rhodamine 6G, rhodamine B, nile blue, neutral red, fluorescein, or quinaldine red.
4. The method according to claim 1, wherein the CDs are CDs with emission wavelengths of 350-700 nm.
5. The method of claim 1, wherein the carbon dot/dye @ metal organic framework composite material is CDs/rh6g@zif-8, CDs/rh6g@uio-66.
6. The preparation method according to claim 1 or 5, wherein the carbon dot/dye @ metal organic framework composite material is CDs/rh6g@zif-8, and the preparation method comprises the following steps: 2-methylimidazole and zinc nitrate are respectively dissolved in methanol, the obtained zinc nitrate solution is dripped into the 2-methylimidazole solution, CDs and rhodamine 6G are immediately added after the dripping is finished, and the mixture is stirred and mixed uniformly and then is kept stand for 12 to 36 hours, so that CDs/Rh6G@ZIF-8 orange red powder is obtained.
7. The preparation method according to claim 1, wherein the carbon dot/dye@metal organic framework composite material is CDs/rh6g@uio-66, and the preparation method comprises the following steps: respectively dissolving terephthalic acid and sodium acetate in N, N-dimethylformamide, uniformly mixing the obtained two solutions by ultrasonic, adding zirconium tetrachloride, continuing ultrasonic until the zirconium tetrachloride is completely dissolved, then adding CDs and Rh6G into the solution, transferring the mixed liquid into a reaction kettle, and heating for reaction to obtain CDs/Rh6G@UiO-66 orange-red powder.
8. A carbon dot/dye @ metal organic framework composite material prepared by the method of any one of claims 1-7.
9. Use of a carbon dot/dye @ metal organic framework composite material prepared by a method according to any one of claims 1 to 7 for detection of mercury ions by a ratiometric fluorescent probe.
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