CN108977198A - A kind of method that lignin prepares single crystal graphene quantum dot - Google Patents
A kind of method that lignin prepares single crystal graphene quantum dot Download PDFInfo
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Abstract
A kind of method that lignin prepares single crystal graphene quantum dot, this method is by carrying out nitric acid and hydro-thermal process to lignin, it is 3.73nm that average grain diameter, which can be prepared, graphene quantum dot with obvious single crystal graphene lattice, simultaneously, by adjusting reaction condition, it can be achieved that the particle size of graphene quantum dot and the controllable preparation of different fluorescence emission wavelengths.The graphene quantum dot quantum yield being prepared is up to 22%, up-conversion luminescence property near infrared region response, gained quantum dot is applied to polychrome bio-imaging, show good imaging effect, it can be widely applied to numerous areas, such as bioprobe, bio-sensing, Nano medication, photocatalysis and light emitting diode preparation.The one-step method prepares single crystal graphene quantum dot simply, effectively, inexpensively using lignin, the higher value application of lignin can be achieved, enterprise can be refined in papermaking and biomass with large-scale application, can be high-valued graphene quantum dot material by production waste material lignin conversion.
Description
Technical field
The preparation method of the present invention relates to a kind of single crystal graphene quantum dot based on lignin, specifically passes through nitre
Acid oxidase cutting and hydrothermal carbonization processing obtain partial size in 2-6nm, and average grain diameter is the graphene quantum dot of 3.73nm, quantum
Yield is up to 22%, the up-conversion luminescence property near infrared region response, by adjusting reaction condition, it can be achieved that graphene amount
The particle size of son point and the controllable preparation of different fluorescence emission wavelengths.
Background technique
Graphene quantum dot is a kind of partial size in the novel zero dimension carbon material of 1-10nm, is compared with conventional semiconductors quantum dot
It with good biocompatibility and smaller toxicity, is usually made of 1-3 layers of graphene, there is apparent graphene lattice.
Due to the up-conversion luminescence property that its special Photoluminescence and near infrared region respond, make graphene quantum dot biology at
Picture, bio-sensing, Nano medication, photocatalysis and light emitting diode preparation etc. have huge application prospect.Synthesis at present
The method of graphene quantum dot has " method from top to bottom ", i.e., passes through oxidation stripping using raw materials such as graphene, carbon nanotube and graphite
From the methods of big class graphene-structured is cut into graphene quantum dot, in addition, in recent years, occur successively " from bottom to top
Method " is i.e. with small organic molecule by the methods of hydrothermal carbonization pyrolysis synthesizing graphite alkene quantum dot, however, current method is generally deposited
Raw material costly, raw material is non-renewable, and the graphene quantum dot quantum yield prepared is not high, most of 10% or so
(Li,L.L.Ji,J.Fei,R.Wang,C.Z.Lu,Q.Zhang,J.R.Jiang,L.P.Zhu,J.J.Advanced
Functional Materials 2012,22,2971.) and graphene lattice it is unobvious the disadvantages of.
For lignin for traditional papermaking enterprise and biomass refining enterprise, the byproduct for being often thought of as production is useless
Material, current 90% lignin usually all burned as fuel, but as aromatic compound resource the most abundant in nature,
There is a large amount of phenyl ring in lignin structure, and there are great application values, but at present to the lignin quilt only less than 2%
Be made into the low-value products such as dispersing agent, surfactant (Zakzeski, J.Bruijnincx, P.C.A.Jongerius, A.L.,
Et al.Chemical Reviews 2010,110,3552.), therefore how to realize that the higher value application of lignin is urgently to solve
Certainly.
Summary of the invention
The present invention is in view of the above shortcomings of the prior art, it is desirable to provide it is a kind of by lignin conversion be single crystal graphene quantum
The lignin conversion of low value is the technical problem to be solved is that cheap, efficient, magnanimity high added value by the technology of point,
The single crystal graphene quantum dot of high quality.
A kind of method that lignin prepares single crystal graphene quantum dot, it is characterised in that this method in accordance with the following steps into
Row:
(1) lignin nitric acid treatment: lignin is handled with concentrated nitric acid, makes its oxidative degradation, is cut to wooden plain piece
Section.
(2) hydrothermal carbonization: the lignin after nitric acid oxidation being placed in 180 DEG C of baking ovens and reacts 12h, reaction solution is diluted,
Dialysis is graphene quantum dot solution to remove remaining sour and other impurity metal ions, the solution after dialysis, and freeze-drying is
Obtain graphene quantum dot.
(3) size regulates and controls: the time by reducing hydrothermal carbonization, the lignin after nitric acid oxidation being placed at 180 DEG C of bakings
1h is reacted in case, reaction solution is diluted, and size grain can be prepared to remove remaining acid and other impurity metal ions in dialysis
The graphene quantum dot of diameter bigger (average grain diameter 4.40nm), while there is red shift in its fluorescence emission wavelengths.
The present invention has the following advantages and outstanding effects:
(1) it the present invention provides the technology that lignin conversion can be single crystal graphene quantum dot by one kind, realizes honest and clean
It is to valence, efficient, magnanimity the single crystal graphene quantum dot of high added value, high quality, this method by the lignin conversion of low value
It can be by the enterprises such as papermaking enterprise and biorefinery large-scale use.
(2) graphene quantum dot of the two kinds of partial sizes of the invention obtained by the differential responses time, fluorescence emission wavelengths can
Realize controllable offset, the quantum dot average grain diameter for reacting 1h is 4.40nm, and the quantum dot average grain diameter of 12h is 3.73nm,
On fluorescence emission wavelengths, the quantum dot for reacting 1h is 406nm, and the quantum dot of 12h is 429nm, can be made by the differential responses time
The graphene quantum dot of standby different-grain diameter, to realize the regulation of its fluorescence emission wavelengths.
Detailed description of the invention
Fig. 1 is the size statistic and transmission electron microscope photo of graphene quantum dot prepared by embodiment 1.
Fig. 2 is the graphene quantum dot transmission electron microscope of the two kinds of partial sizes obtained under the differential responses time prepared by embodiment 2
And partial size statistics.
Fig. 3 is the graphene quantum dot fluorescence spectrum of the two kinds of partial sizes obtained under the differential responses time prepared by embodiment 2
Characterization result.
Fig. 4 is the XRD characterization of graphene quantum dot prepared by embodiment 1.
Fig. 5 is the Raman characterization of graphene quantum dot prepared by embodiment 1.
Fig. 6 is the optical property characterization of graphene quantum dot prepared by embodiment 1
Fig. 7 is the experiment flow figure of graphene quantum dot prepared by embodiment 1
Specific embodiment
Embodiment 1
(1) lignin nitric acid treatment: the concentrated nitric acid of 5mL 65wt% being added dropwise to 3.3684g alkali lignin, is slowly dripping
It during entering concentrated nitric acid, is stirred continuously with glass bar, adds 15mL deionized water after nitric acid is added dropwise, stir evenly and stand
12h。
(2) hydrothermal carbonization: the reaction solution 7mL after taking nitric acid treatment is placed in the polytetrafluoroethylene (PTFE) of 25mL stainless steel cauldron
In gallbladder, it is placed in hydro-thermal reaction 12h in 180 DEG C of baking ovens.Gained reaction solution is diluted, with the bag filter of 3000 molecular weight be placed in from
Dialyse in sub- water 5 days with remove it is remaining acid and other impurity metal ions, the solution after dialysis be that graphene quantum dot is molten
Liquid is lyophilized up to graphene quantum dot.
Embodiment 2
Processing method is with example 1, except that then adopting hydro-thermal reaction 1h in 180 DEG C of baking oven is placed in step (2)
It is dialysed with same method, freeze-drying.
Embodiment 3
Graphene quantum dot is characterized:
(1) Electronic Speculum characterizes: gained graphene quantum dot solution deposits in micro-grid, characterizes quantum with transmission electron microscope after drying
Point pattern, partial size and lattice (attached drawing 1a), and graphene quantum dot particle size and its distribution are counted, partial size 2-6nm is average
Partial size is 3.73nm (attached drawing 1d, on), and lattice 0.21nm corresponds to graphene 1100 crystal face (attached drawing 1b) electronic diffraction chart
Face, gained.(attached drawing 1c) is characterized by AFM;Size statistic is statistics indicate that (attached drawing 1d, under) is the 1-3 layer graphite of 1-2nm thickness
Alkene, average height 1.37nm.
(2) size control: the quantum point grain diameter for reacting 1h is larger (attached drawing 2a), the smaller (attached drawing of the quantum point grain diameter of 12h
2c), quantum dot particle size and its distribution are counted, average grain diameter is respectively 4.40nm (attached drawing 2d), 3.73nm (attached drawing 2b),
On fluorescence emission wavelengths, the quantum dot for reacting 1h is 406nm, and the quantum dot of 12h is 429nm, can be made by the differential responses time
The graphene quantum dot of standby different-grain diameter, to realize the regulation (attached drawing 3) of its fluorescence emission wavelengths.
(3) XRD characterization: obtained graphene quantum dot has a spike in 2 θ=26.5 °, and interlamellar spacing isWith
The crystal face of graphite is consistent (attached drawing 4).
(4) Raman is characterized: the intensity ratio at the peak D and the peak G is 0.94 (attached drawing 5).
(5) fluorescence spectrum characterization: intense green fluorescence (attached drawing 6a, interior illustration) is issued to graphene quantum dot solution, most
Being suitble to excitation wavelength is 310nm, and most strong launch wavelength is 406nm (attached drawing 6b), the upper conversion hair with near-infrared region response
Light property (attached drawing 6d), optimum PH 7 is more sensitive to acidic environment (attached drawing 6e), and ultraviolet stability is good (attached drawing 6f).
(6) Fig. 7 is the experiment flow figure that preparation is prepared graphene quantum dot by lignin.
Claims (11)
1. a kind of method that lignin prepares single crystal graphene quantum dot, it is characterised in that can by the hydrothermal carbonization to lignin
Prepare average grain diameter be 3.73nm single crystal graphene quantum dot, adjust reaction condition, it can be achieved that graphene quantum dot partial size
The controllable preparation of size and different fluorescence emission wavelengths, this method is simple, cheap, papermaking enterprise and biomass can be refined enterprise
The lignin waste material of generation utilizes on a large scale, high financial profit.
2. the graphene quantum dot of method preparation as described in claim 1, it is characterised in that the lignin raw material is selected from alkali
Lignin, lignosulfonates, kraft lignin, preferably alkali lignin.
3. preparation method as described in claim 1, it is characterised in that this method carries out in accordance with the following steps:
(1) lignin nitric acid treatment: nitric acid oxido-degradation lignin is cut to lignin segment.
(2) hydrothermal carbonization: the lignin after nitric acid oxidation being placed in 180 DEG C of baking ovens and reacts 12h, reaction solution is diluted, dialysis
To remove remaining acid and other impurity metal ions, by reducing the reaction time, it is bigger (average that size can be prepared
Partial size is 4.40nm) graphene quantum dot, while there is red shift in its fluorescence emission wavelengths.
4. processing method as claimed in claim 3, it is characterised in that the inorganic acid is selected from nitric acid, sulfuric acid, phosphoric acid, preferably
Nitric acid.
5. nitric acid treatment method as claimed in claim 3, it is characterised in that the processing time be selected from 30min, 1h, 3h,
6h, 9h, 12h, preferably 12h.
6. processing method as claimed in claim 3, it is characterised in that the reaction temperature is selected from 160 DEG C, 180 DEG C, 200
DEG C, preferably 180 DEG C.
7. difference size graphite alkene quantum dot as claimed in claim 3, it is characterised in that its fluorescence property and its size
Closely related, size is bigger, and fluorescence emission wavelengths red shift is bigger, which can be widely applied in different field.
8. the graphene quantum dot of method preparation as claimed in claim 3, it is characterised in that its quantum yield is up to 22%,
There is up-conversion luminescence property in near-infrared region, this has important application value to bio-imaging.
9. the graphene quantum dot of method preparation as claimed in claim 3, it is characterised in that its best pH value is 7, this correspondence
It is had potential application for people or other mammals.
10. the graphene quantum dot of method preparation as claimed in claim 3, it is characterised in that its best pH value is 7, this correspondence
It is had potential application for people or other mammals.
11. the graphene quantum dot of method preparation as claimed in claim 3, it is characterised in that in alkaline condition, fluorescence is not strong for it
Degree variation is little, but Strength Changes are larger in acid condition, can be used in acid PH response apparatus.
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Cited By (6)
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CN110054170A (en) * | 2019-04-19 | 2019-07-26 | 华中科技大学 | A kind of method and product using lignin preparation carbon quantum dot |
CN110589811A (en) * | 2019-09-04 | 2019-12-20 | 广东工业大学 | Lignin-based graphene quantum dot material and preparation method and application thereof |
CN110615426A (en) * | 2019-11-20 | 2019-12-27 | 中国科学院长春光学精密机械与物理研究所 | Carbon nanodot with thermal activation near-infrared up-conversion luminescence characteristic and preparation method and application thereof |
CN111019650A (en) * | 2019-12-17 | 2020-04-17 | 中原工学院 | Synthesis method and application of red fluorescent carbon dots |
CN111039280A (en) * | 2019-12-16 | 2020-04-21 | 华南理工大学 | Lignin-based graphene quantum dot and preparation method and application thereof |
CN115676811A (en) * | 2022-11-07 | 2023-02-03 | 河南农业大学 | Method for preparing graphene from lignin |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110054170A (en) * | 2019-04-19 | 2019-07-26 | 华中科技大学 | A kind of method and product using lignin preparation carbon quantum dot |
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CN110615426A (en) * | 2019-11-20 | 2019-12-27 | 中国科学院长春光学精密机械与物理研究所 | Carbon nanodot with thermal activation near-infrared up-conversion luminescence characteristic and preparation method and application thereof |
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CN111019650B (en) * | 2019-12-17 | 2022-11-01 | 中原工学院 | Synthesis method and application of red fluorescent carbon dots |
CN115676811A (en) * | 2022-11-07 | 2023-02-03 | 河南农业大学 | Method for preparing graphene from lignin |
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