CN105567227B - A kind of method that graphene quantum dot is extracted in the solid waste from coffee grounds - Google Patents
A kind of method that graphene quantum dot is extracted in the solid waste from coffee grounds Download PDFInfo
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- CN105567227B CN105567227B CN201610026439.0A CN201610026439A CN105567227B CN 105567227 B CN105567227 B CN 105567227B CN 201610026439 A CN201610026439 A CN 201610026439A CN 105567227 B CN105567227 B CN 105567227B
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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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
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention relates to the preparation method that fluorescence graphene quantum dot material is extracted in a kind of solid waste from coffee grounds.It is carbon source that the present invention, which selects coffee grounds solid waste cheap and easy to get, and substantial amounts of water-soluble graphene quantum dots are can obtain by simple water-heat process.The quantum dot that the present invention synthesizes can be stably dispersed in water, be light yellow under low concentration, brown under high concentration（Concentration is bigger, and color is deeper）；The particle size of the graphene quantum dot obtained is 37 nm, and surface carries substantial amounts of carboxyl and amido, beneficial to later surface-functionalized, can bring multiduty application, while show superior fluorescence property：The quanta point material that the present invention synthesizes shows tempting application prospect in high-technology fields such as environmental protection, bio-nanotechnology, new energy, nano-devices, and synthetic method is simple and environmentally-friendly, quick, simple, low energy consumption, is adapted to industry amplification.
Description
Technical field
The invention belongs to field of material preparation, is related in a kind of solid waste from coffee grounds and extracts graphene quantum dot
Method.
Background technology
Illuminant nanometer material is in fields such as tumour visualization treatment, photolysis water hydrogen and quantum dot sensitized solar cells
All there is important application value.Wherein, fluorescence graphene quantum dot material is as the grapheme material to receive much concern in recent years
Middle minimal structure material receives much concern.To so extra small zero-dimensional system, the carrier of massless in three dimensions by
Strong quantum confinement effect, it will cause grapheme material many interesting, adjustable new property, new effect and new opplications.
Compared with traditional semiconductor-quantum-point fluorescent material, new graphene quantum dot has the excellent of many uniquenesses
Gesture, such as environment-friendly --- without highly toxic metallic element such as cadmium, lead；Steady chemical structure --- resistance to strong acid, highly basic, it is resistance to
Photoetch；It is surface-functionalized easily to realize --- common solvents are stably dispersed in, meet the need of material low cost working process
Ask.But as a kind of emerging nano material, there is the report much on graphene quantum dot preparation method at present.Mesh
The water-soluble graphene quantum dots synthetic method of preceding report includes " from bottom to top " and " from top to bottom " two classes.Although graphene amount
The synthetic method of son point has remarkable progress, but from the point of view of large-scale production graphene quantum dot, these methods are all
It there are problems that many, be mainly manifested in that the synthetic yield of graphene quantum dot is very low, prepared by gram quantity on a laboratory scale
Also highly difficult, some synthesis steps are excessively cumbersome, even with equipment costly and auxiliary reagent etc..If these are asked
Topic can not solve very well, and the large-scale application of graphene quantum dot will be unable to realize.Therefore one kind is explored simply, inexpensively, efficiently
The method for being adapted to large-scale production graphene quantum dot is a very challenging job.
The content of the invention
It is an object of the invention to solve problems of the prior art, there is provided be carried in a kind of coffee grounds solid waste
The method for taking graphene quantum dot, this method step is simple, cost is cheap, is easier to preparation, yield height.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that.
A kind of method that coffee grounds solid waste prepares graphene quantum dot, it is characterised in that the specific steps of this method
For：
A. it is super to be stirred in 0.05 ~ 0.1 mol/L watery hydrochloric acid obtained coffee grounds 1g 80 ml concentration of addition will to be reclaimed
Sound surface active 2-20h；
B. ultrasound is stopped, filtering, it is about 7 to wash coffee grounds to filtrate pH value repeatedly with deionized water；
C. by the coffee grounds solid after washing in 100 ml distilled water ultrasonic disperse, while stirring add 1-10 ml ammonia
The mixed liquor of water and 5-40 ml hydrazine hydrates（The pH of solution is not less than 12）, it is immediately placed in ptfe autoclave, 120
~200 o5 ~ 20 h are reacted at a temperature of C；
D. taken out after natural cooling, with 25 nm membrane filtrations, the black solid of some is remained on filter membrane（Can be further
Recycle）, stable dispersion the graphene quantum dot of substantial amounts of hyperfluorescence in dark brown filtrate；
E. the solution after filtering is transferred in bag filter and dialysed, by solution 120oDried under C, finally obtain brown ash
The graphene quantum dot powder of color.
Above-mentioned coffee grounds includes depth, moderate and coffee grounds caused by the coffee that slightly bakees.
Advantages of the present invention and feature
It is raw material that the inventive method, which selects inexpensive coffee grounds, and being successfully realized turns waste into wealth --- activated by acid oxidase
Coffee grounds surface, then hydro-thermal the water-soluble graphene quantum dots of high fluorescent brightness are prepared.Coffee is a kind of inbred crops,
There is plantation all over the world.Coffee will graphitization after bakeing.And these graphite during baking
Peeled off well, form the class graphene-structured of few layer.By simple acid activation and hydro-thermal process, these classes can be made
The material of graphene-structured forms graphene quantum dot.Graphene quantum dot size is small（3—7 nm）, thickness is 0.5-4 nm,
The number of plies is 1-8 layers；The surface carboxyl groups functional group of quantum dot ensure that the water solubility of quantum dot, i.e., can still divide well after the drying
Dissipate in the aqueous solution.Process steps are simple, without introducing surface passivator（Surface can form the water-soluble function such as amido and carboxyl
Group）, without sophisticated equipment, reaction is extremely gentle, and energy consumption is low, and yield is high, is especially suitable for the industry amplification of low cost.
Brief description of the drawings
Fig. 1 is the preparation flow figure of fluorescence graphene quantum dot prepared by the preferred embodiment of the present invention.
Fig. 2 is the atomic force microscope images of graphene quantum dot prepared by the preferred embodiment of the present invention（It is left）And Flied emission
Transmission electron microscope picture（It is right）.
Fig. 3 is the infrared spectroscopic imaging of graphene quantum dot prepared by the preferred embodiment of the present invention（a）, x-ray powder spreads out
Penetrate figure（b）And Raman spectrum（c）.
Fig. 4 is the uv-visible absorption spectra of fluorescence graphene quantum dot prepared by the preferred embodiment of the present invention, fluorescence Spectra
And fluorescence excitation spectrum.Illustration is optics picture of the graphene quantum dot aqueous solution in the case where visible ray and 360 nm are ultraviolet.
Fig. 5 is picture of the fluorescence graphene quantum dot to Hela cell imagings of preferred embodiment of the present invention preparation.
Embodiment
In order to be better understood from the present invention, further illustrated by example.
Embodiment 1
The obtained coffee grounds of slight baking will be reclaimed to clean, 1g is weighed and be added in the mol/L watery hydrochloric acid of 80ml 0.1 and stir
Mix ultrasonic 20h.After ultrasound stops, filtering, it is about 7 to wash coffee grounds to filtrate pH value repeatedly with deionized water.After washing
Coffee grounds solid in 100 ml distilled water ultrasonic disperse, add the mixing of 10 ml ammoniacal liquor and 40 ml hydrazine hydrates while stirring
Liquid（The pH of solution is not less than 12）, it is immediately placed in ptfe autoclave, 200o20h is reacted at a temperature of C.Treat nature
Taken out after cooling, with 25 nm membrane filtrations, obtain dark brown filtrate.Solution after filtering is transferred in bag filter and dialysed, will
Solution is put into baking oven 120 oCDrying, finally obtain the graphene quantum dot powder of taupe.
Embodiment 2
The coffee grounds for reclaiming obtained moderate baking is cleaned, 1g is weighed and is added in the mol/L watery hydrochloric acid of 80ml 0.05
Stir ultrasonic 10h.After ultrasound stops, filtering, it is about 7 to wash coffee grounds to filtrate pH value repeatedly with deionized water.Will washing
The ultrasonic disperse in 100 ml distilled water of coffee grounds solid afterwards, the mixed of 5 ml ammoniacal liquor and 20 ml hydrazine hydrates is added while stirring
Close liquid（The pH of solution is not less than 12）, it is immediately placed in ptfe autoclave, 150o10h is reacted at a temperature of C.Treat certainly
So taken out after cooling, with 25 nm membrane filtrations, obtain dark brown filtrate.Solution after filtering is transferred in bag filter and dialysed,
Solution is put into baking oven 120 oCDrying, finally obtain the graphene quantum dot powder of taupe.
Embodiment 3
The coffee grounds that obtained depth bakees will be reclaimed to clean, 1g is weighed and be added in the mol/L watery hydrochloric acid of 80ml 0.1 and stir
Mix ultrasonic 2h.After ultrasound stops, filtering, it is about 7 to wash coffee grounds to filtrate pH value repeatedly with deionized water.After washing
Coffee grounds solid ultrasonic disperse in 100 ml distilled water, the mixed liquor of 1 ml ammoniacal liquor and 5 ml hydrazine hydrates is added while stirring
（The pH of solution is not less than 12）, it is immediately placed in ptfe autoclave, 120o5h is reacted at a temperature of C.Treat natural cooling
After take out, with 25 nm membrane filtrations, obtain dark brown filtrate.Solution after filtering is transferred in bag filter and dialysed, by solution
It is put into baking oven 120 oCDrying, finally obtain the graphene quantum dot powder of taupe.
Obtained sample is characterized through instrument detection in the present embodiment, and its result is as follows：
Utilize graphene quantum dot made from atomic force microscope observation step e, it can be seen that its thickness is 2 rans
（See Fig. 2 left sides）.Utilize graphene quantum dot made from Flied emission transmission electron microscope observation step e, it can be seen that its size
About 3 nanometers（See Fig. 2 right sides）.The surface functional group of graphene quantum dot made from the present embodiment is measured using infrared spectrometer, can
Contain the hydrophilic functional groups such as hydroxyl, amido and carboxyl to obtain the surface of graphene quantum dot（See Fig. 3）.Utilize UV, visible light
Graphene quantum dot made from light spectrophotometer and fluorescence spectrophotometer measurement the present embodiment, it can be seen that graphene quantum
Point fluorescence emission peak at 470 nanometers,（Referring to Fig. 4）.Fluorescence graphene quantum dot product introduction manufactured in the present embodiment, graphite
The outward appearance of alkene quantum dot colloidal solution；Blue-fluorescence is sent under the irradiation of 365 nano-ultraviolet lights（Referring to Fig. 4 illustrations）.With made stone
Black alkene quantum dot can be used for cell imaging（Referring to Fig. 5）.
Claims (2)
1. the method for graphene quantum dot is extracted in a kind of solid waste from coffee grounds, it is characterised in that there is following preparation
Process and step：
A. coffee grounds 1g recovery obtained is added in the watery hydrochloric acid that 80ml concentration is 0.05~0.1mol/L and is stirred ultrasonic surface
Activate 2-20h；
B. ultrasound is stopped, filtering, it is 7 to wash coffee grounds to filtrate pH value repeatedly with deionized water；
C. by the coffee grounds solid after washing in 100ml distilled water ultrasonic disperse, add 1-10ml ammoniacal liquor and 5- while stirring
The mixed liquor of 40ml hydrazine hydrates, the pH of solution are not less than 12, are immediately placed in ptfe autoclave, in 120~200 DEG C of temperature
5~20h of the lower reaction of degree；
D. taken out after natural cooling, with 25nm membrane filtrations, remain the black solid of some on filter membrane, can further reclaim profit
With stable dispersion the graphene quantum dot of substantial amounts of hyperfluorescence in dark brown filtrate；
E. the solution after filtering is transferred in bag filter and dialysed, solution is dried at 120 DEG C, finally obtains the stone of taupe
Black alkene quantum dot powder.
2. the method for graphene quantum dot is extracted in coffee grounds solid waste according to claim 1, it is characterised in that：
Coffee grounds described in step a includes depth, moderate and the coffee bean that slightly bakees and prepares coffee grounds caused by coffee.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106054492A (en) * | 2016-07-10 | 2016-10-26 | 上海大学 | Graphene quantum dot optical fiber amplifier |
| CN106629658A (en) * | 2016-11-12 | 2017-05-10 | 兰州大学 | Preparation method of fluorescent carbon quantum dot |
| CN107324315A (en) * | 2017-06-07 | 2017-11-07 | 陕西科技大学 | A kind of preparation method of the graphene quantum dot based on leather castoff |
| WO2019040005A1 (en) * | 2017-08-25 | 2019-02-28 | Nanyang Technological University | Functionalised graphene quantum dots as catalysts for biomass conversion |
| KR102197683B1 (en) * | 2018-11-02 | 2021-01-04 | 그래핀스퀘어 주식회사 | A process for manufacturing graphene quantum dots and graphene quantum dots prepared therefrom |
| KR20200106374A (en) * | 2019-03-04 | 2020-09-14 | 주식회사 아이파트너즈 | Carbon-containing materials obtained from spent coffee ground, method for manufacturing the same and use of the same |
| CN110773124A (en) * | 2019-11-06 | 2020-02-11 | 天津城建大学 | Preparation method and application of coffee grounds hydrothermal carbon adsorbent |
| WO2021241785A1 (en) * | 2020-05-29 | 2021-12-02 | 김태규 | Method for manufacturing carbon material using spent coffee grounds |
| CN115125001B (en) * | 2022-08-23 | 2023-04-28 | 济南大学 | Preparation method of green luminous carbon dots |
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| KR101405006B1 (en) * | 2012-05-29 | 2014-06-10 | (주)엔엘피 | Coffee residue points made in the manufacture of light-emitting carbon nanotubes and method of manufacture |
| CN103320125B (en) * | 2013-06-06 | 2016-06-29 | 上海大学 | The preparation method of multicolor fluorescence graphene quantum dot material |
| CN104694119A (en) * | 2013-12-06 | 2015-06-10 | 中国科学院大连化学物理研究所 | Functional fluorescent carbon dot as well as preparation method and application thereof |
| CN104650864B (en) * | 2015-03-04 | 2017-03-01 | 东华大学 | A kind of preparation method of biomass-based carbon quantum dot |
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