CN106938842A - It is a kind of to be pyrolyzed the method that citric acid prepares graphene quantum dot - Google Patents

It is a kind of to be pyrolyzed the method that citric acid prepares graphene quantum dot Download PDF

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Publication number
CN106938842A
CN106938842A CN201610001048.3A CN201610001048A CN106938842A CN 106938842 A CN106938842 A CN 106938842A CN 201610001048 A CN201610001048 A CN 201610001048A CN 106938842 A CN106938842 A CN 106938842A
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gqds
quantum dot
graphene quantum
citric acid
pyrolyzed
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王翔
王培�
陈晨
蒙正彦
齐东来
张坤
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/90—Other crystal-structural characteristics not specified above
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The graphene quantum dot (b GQDs) of blue light-emitting is prepared by being pyrolyzed citric acid, and further hydro-thermal process obtains blue-green fluorescent quantum dot (g GQDs).Pass through ultraviolet-visible absorption spectroscopy (UV vis), fluorescence spectrum (PL), Fourier transform infrared spectroscopy (FTIR), x-ray photoelectron power spectrum (XPS) and X-ray diffraction (XRD) are characterized and tested to the GQDs of preparation Structural and optical characterization.

Description

It is a kind of to be pyrolyzed the method that citric acid prepares graphene quantum dot
Technical field
The invention belongs to inorganic nano material graphene quantum dot (GQDs) preparation field, it is related to a kind of method that pyrolysis citric acid prepares graphene quantum dot.
Background technology
Graphene (graphene) is a kind of sp2The single layer of carbon atom of orbital hybridization it is tightly packed into bi-dimensional cellular shape carbonaceous new material, with specific surface area is big, electrical and thermal conductivity is good, high mechanical strength, the advantages of good biocompatibility.Quantum dot (quantum dots, QDs) it is the nanocrystals that are made up of II-VI races of race or III-V group element, have the advantages that the optical property and dimensional effect of uniqueness and fluorescence lifetime are long, it is all had wide practical use in terms of biology, environment, medical science.Graphene quantum dot (GQDs) is used as a kind of new fluorescent nano material, compared with traditional semiconductor-quantum-point, GQDs has preferable water-soluble, chemical inertness, biocompatibility and hypotoxicity and the structure with graphene and edge effect, make it be widely used in bio-imaging, drug delivery, environment measuring.The GQDs such as Dong handles human breast cancer MCF-7 cell, and Wang etc. utilizes GQDs to Cu2+Detected.
GQDs mainly has (top-down) from top to bottom and from bottom to top (bottom-up) two kinds of preparation methods.It is a kind of simple, quick and economic synthetic method by being pyrolyzed organic precursor to obtain GQDs, currently reported use glucose, citric acid etc., which is cracked, is made GODs.
This experiment is used as presoma from citric acid, GQDs is obtained by heating cracking, and its pattern, structure, composition and fluorescent characteristic are studied, then hydro-thermal process has obtained turning blue the g-GQDs of green fluorescence, and contrasted it with the b-GQDs of blue-fluorescence, the influence to GQDs photoluminescent properties such as temperature, time, pH, solvent is have studied, direction is provided for the application in detection of heavy metal ion of graphene quantum dot.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of method that pyrolysis citric acid prepares graphene quantum dot.This method prepares the graphene quantum dot (b-GQDs) of blue light-emitting by being pyrolyzed citric acid first, and further hydro-thermal process obtains blue-green fluorescent quantum dot (g-GQDs).Pass through ultraviolet-visible absorption spectroscopy (UV-vis), fluorescence spectrum (PL), Fourier transform infrared spectroscopy (FTIR), x-ray photoelectron power spectrum (XPS) and X-ray diffraction (XRD) are characterized and tested to the GQDs of preparation Structural and optical characterization.
The present invention relates to pyrolysis citric acid prepare the detailed process of graphene quantum dot, including：
(1) blue light-emitting GQDs preparation
2g citric acids are weighed in 50mL round-bottomed flasks, at 200 DEG C, now liquid is changed into after crocus, stop heating.By above-mentioned yellow liquid, 100mL NaOH solutions (10mg mL are added-1) in, 15min is stirred, finally pH is adjusted to neutrality with 1: 10 dilute nitric acid solution, then the further dialysis purifications of GQDs is handled with bag filter, obtained filtrate is dried in vacuo and can obtain GQDs solids.
(2) GQDs hydro-thermal process
By the 20mL GQDs aqueous solution obtained above, adjusted with NaOH to pH=12, above-mentioned solution is transferred in 50mL reactors, 12h is reacted at 180 DEG C.
The above by the form of embodiment again to the present invention is described in further detail below, but this should not be interpreted as to the scope of above-mentioned theme of the invention and be limited only to following embodiment, all technologies realized based on the above of the present invention belong to the scope of the present invention.
Embodiment
Embodiment 1
Pyrolysis citric acid prepares graphene quantum dot
2g citric acids are weighed in 50mL round-bottomed flasks.Cross citric acid after a few minutes and start liquefaction, now temperature is about 145 DEG C, liquid is colourless, until temperature is raised to about 180 DEG C, now liquid is light yellow.It is to be heated to 200 DEG C when, now liquid is changed into after crocus, stop heating.Crocus liquid is drawn with glue head dropper, is added in 100mLNaOH solution (10mg/mL), magnetic agitation 15min, finally pH is adjusted to neutrality with dust technology (1: 10).The GQDs solution of acquisition is placed in 4 DEG C of refrigerators and saved backup.In order to which subsequent experimental is characterized, use MWCO that GQDs is made into further dialysis purification for 3500 bag filter.Resulting filtrate, which is dried in vacuo, can obtain GQDs solids.
Embodiment 2：
GQDs hydro-thermal process
The 20mLGQDs aqueous solution obtained above (being adjusted with NaOH to 12) is added in 50mL ptfe autoclaves, 12h is reacted at 180 DEG C.
Embodiment 3：
The test of product and sign
The graphene quantum dot cracked obtained by citric acid is determined into data such as Fig. 1 that XRD and XPS is obtained in 60 DEG C of vacuum drying ovens, after drying, shown in Fig. 2.
The graphene quantum dot ultrasonic disperse for cracking gained after citric acid and hydro-thermal process is tested into its ultra-violet absorption spectrum and fluorescence spectrum, such as Fig. 3, shown in Fig. 4 in secondary water, respectively；Wherein Fig. 3 (b) is corresponding infrared spectrum, and test process will ensure that sample is dried, with spectroscopic pure KBr compressing tablets.
Brief description of the drawings
Fig. 1 GQDs XRD
Fig. 2 GQDs XPS spectrum figure (a) and C1s high-resolution spectrogram (b)
The ultra-violet absorption spectrum (a) and infrared spectrogram (b) of Fig. 3 b-GQDs, g-GQDs and citric acid
Fig. 4 b-GQDs' excites and emission spectrum (a)；B-GQDs and g-GQDs fluorescent exciting spectrogram (b)；B-GQDs (c) and fluorescence spectrums of the g-GQDs (d) under different excitation wavelengths.

Claims (4)

  1. It is chondritic, the nano material under transmission electron microscope 1. graphene quantum dot is a kind of nano material With preferable fluorescence property.
  2. 2. prepare graphene quantum dot：2g citric acids are weighed in 50mL round-bottomed flasks, at 200 DEG C, now liquid Body is changed into after crocus, stops heating.By above-mentioned yellow liquid, 100mL NaOH solutions (10mg is added mL-1) in, 15min is stirred, finally pH is adjusted to neutrality with 1: 10 dilute nitric acid solution, then uses bag filter By the further dialysis purification processing of GQDs, obtained filtrate is dried in vacuo in 60 DEG C of vacuum drying ovens to be obtained To GQDs solids.
  3. 3. carrying out dialysis lock out operation according to the graphene quantum dot that claim is produced to cracking citric acid, use GQDs is made further dialysis purification by MWCO for 3500 bag filter.
  4. 4. in order to further obtain blue-green fluorescent quantum dot (g-GQDs), the blue light graphene amount produced to cracking Son clicks through water-filling heat treatment, and the condition of hydro-thermal process is：The above-mentioned 20mL GQDs aqueous solution is taken, NaOH is used Adjust to pH=12, above-mentioned solution is transferred in 50mL reactors, the hydro-thermal reaction 12h at 180 DEG C.
CN201610001048.3A 2016-01-04 2016-01-04 It is a kind of to be pyrolyzed the method that citric acid prepares graphene quantum dot Pending CN106938842A (en)

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CN107500274A (en) * 2017-10-11 2017-12-22 江苏安纳泰环保科技有限公司 A kind of preparation method of the graphene quantum dot of three primary colors fluorescence
CN107572507A (en) * 2017-10-12 2018-01-12 山西大学 A kind of preparation method of amphipathic graphene quantum dot
CN107601467A (en) * 2017-10-12 2018-01-19 山西大学 A kind of preparation method of oil-soluble graphene quantum dot
CN108336339A (en) * 2018-02-09 2018-07-27 北京新能源汽车股份有限公司 Vanadium cluster polyacid-graphene quantum dot composite material, preparation method and its application
CN108503921A (en) * 2018-05-23 2018-09-07 江南大学 A kind of preparation method of thiocarbamide functionalized nano Graphene antibiosis material
CN108605983A (en) * 2018-04-12 2018-10-02 江苏科技大学 A kind of Fe3O4@GQDs@Ag nucleocapsid composite antibacterial materials and its preparation method and application
CN109286018A (en) * 2018-12-06 2019-01-29 中国科学院兰州化学物理研究所 A kind of preparation method of ultra-thin two-dimension carbon plate
CN109342471A (en) * 2018-12-21 2019-02-15 四川聚创石墨烯科技有限公司 A method of determining carbon material attribute
CN109665514A (en) * 2017-10-17 2019-04-23 江南大学 A kind of Hg2+The preparation method of detection and diagnosing tumor graphene quantum dot
CN111995866A (en) * 2020-07-14 2020-11-27 广东工业大学 Low-dielectric polyimide composite film material and preparation method thereof
CN112897526A (en) * 2021-02-05 2021-06-04 西南大学 Preparation method and application of porous carbon dot material based on industrial glucose
CN115404075A (en) * 2022-09-07 2022-11-29 中国科学院上海微***与信息技术研究所 Magnetic graphene quantum dot and preparation method and application thereof

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* Cited by examiner, † Cited by third party
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CN107500274A (en) * 2017-10-11 2017-12-22 江苏安纳泰环保科技有限公司 A kind of preparation method of the graphene quantum dot of three primary colors fluorescence
CN107500274B (en) * 2017-10-11 2020-05-22 江苏安纳泰环保科技有限公司 Preparation method of graphene quantum dots with three primary colors of fluorescence
CN107572507A (en) * 2017-10-12 2018-01-12 山西大学 A kind of preparation method of amphipathic graphene quantum dot
CN107601467A (en) * 2017-10-12 2018-01-19 山西大学 A kind of preparation method of oil-soluble graphene quantum dot
CN107572507B (en) * 2017-10-12 2020-06-12 山西大学 Preparation method of amphiphilic graphene quantum dots
CN109665514A (en) * 2017-10-17 2019-04-23 江南大学 A kind of Hg2+The preparation method of detection and diagnosing tumor graphene quantum dot
CN108336339A (en) * 2018-02-09 2018-07-27 北京新能源汽车股份有限公司 Vanadium cluster polyacid-graphene quantum dot composite material, preparation method and its application
CN108605983A (en) * 2018-04-12 2018-10-02 江苏科技大学 A kind of Fe3O4@GQDs@Ag nucleocapsid composite antibacterial materials and its preparation method and application
CN108503921A (en) * 2018-05-23 2018-09-07 江南大学 A kind of preparation method of thiocarbamide functionalized nano Graphene antibiosis material
CN109286018A (en) * 2018-12-06 2019-01-29 中国科学院兰州化学物理研究所 A kind of preparation method of ultra-thin two-dimension carbon plate
CN109342471A (en) * 2018-12-21 2019-02-15 四川聚创石墨烯科技有限公司 A method of determining carbon material attribute
CN111995866A (en) * 2020-07-14 2020-11-27 广东工业大学 Low-dielectric polyimide composite film material and preparation method thereof
CN111995866B (en) * 2020-07-14 2023-08-15 广东工业大学 Low-dielectric polyimide composite film material and preparation method thereof
CN112897526A (en) * 2021-02-05 2021-06-04 西南大学 Preparation method and application of porous carbon dot material based on industrial glucose
CN115404075A (en) * 2022-09-07 2022-11-29 中国科学院上海微***与信息技术研究所 Magnetic graphene quantum dot and preparation method and application thereof

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Application publication date: 20170711