CN109023520A - A kind of method that black liquid prepares high quality single crystal graphene - Google Patents
A kind of method that black liquid prepares high quality single crystal graphene Download PDFInfo
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- CN109023520A CN109023520A CN201810776568.0A CN201810776568A CN109023520A CN 109023520 A CN109023520 A CN 109023520A CN 201810776568 A CN201810776568 A CN 201810776568A CN 109023520 A CN109023520 A CN 109023520A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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Abstract
A kind of method that black liquid prepares single crystal graphene, this method is by carrying out hydro-thermal process to black liquid, 2.5 μm of average grain diameter can be prepared, full-size is up to 5 μm with obvious single crystal graphene lattice high-quality graphene piece, simultaneously, by the simple adjustment reaction time, it can be achieved that the controllable preparation of the different sizes, different surfaces state and pore structure of graphene.The graphene average-size being prepared can be from 0.3 to 2.5 μm, can be widely applied to numerous areas, such as battery, supercapacitor, catalysis and absorption field.This method is with one-step method by biomass waste material, black liquid is converted into high quality single crystal graphene, this method it is simple, cheap, environmentally protective, it can be achieved that black liquid higher value application, and high-valued grapheme material can be converted by production waste material black liquid with large-scale application in papermaking.
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 one
Hydrothermal carbonization processing is walked, has obtained average-size at 2.5 μm, the graphene film that full-size is 5 μm, and it is anti-by simple adjustment
, it can be achieved that from 0.3 to 2.5 μm of average-size of simple controllable preparation of graphene between seasonable.
Background technique
Graphene has sp as one of new carbon of greatest concern in recent years2The carbon atom of hydridization is connected with each other
The monolayers thick bi-dimensional cellular shape structure of formation, the excellent electricity of special construction bring, power, light, machinery and hot property, each
It is greatly paid close attention in a field.The common preparation method of graphene includes mechanical stripping, chemical vapor deposition (CVD), oxidation
Reduction, dissolution thermal method removing, organic synthesis etc..At present laboratory it is the most commonly used, it is effective, can the approach of macroscopic preparation of graphene be
Graphene oxide is prepared by chemical oxidation and removing, then this method is due to needing a large amount of strong oxidizer, oxidation process band
The oxygen-containing functional groups such as hydroxyl, the epoxy come, inevitably bring more defect, i.e. table to the perfect lattice structure of graphene
There are many sp in face3The amorphous carbon structure of hydridization can also restrict graphite significantly while greatly reducing the quality of graphene
The performances such as alkene material electricity, optics, mechanics.Therefore, how the single crystal graphene of large scale preparation high quality is urgently to be solved.
CVD is one of the preparation method of high quality single crystal graphene emerging in recent years, with gas molecules such as methane in gold
Belong to deposition carbon on matrix and prepare graphene, but this method needs stringent complicated reaction condition, higher temperature, high-purity gas
The use of body, special metallic matrix and special installation is but also the preparation method higher cost, it is often more important that, this method pair
The transfer of graphene is still difficult to solve.In addition, other preparation methods developed in recent years such as electrochemistry up-stripping, You Jihe
At the methods of remain synthesize complex, higher cost, and preparation graphene quality it is lower the problems such as.It is how real
Existing the simple, cheap of graphene, high quality controllable preparation become a problem urgently to be resolved
Black liquid is often thought of as the byproduct waste material of production, at present for making for traditional papermaking enterprise
Paper black liquor using usually all being burned as fuel, contain a large amount of lignin in black liquid, but it is as in nature
The most abundant aromatic compound resource, there is a large amount of phenyl ring in lignin structure, and there are great application values, but at present
To the lignin 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 black liquor is urgently to be resolved.
Summary of the invention
The present invention is in view of the above shortcomings of the prior art and the problems such as the devalued utilization of black liquid, it is desirable to provide one
Kind converts black liquid to the technology of single crystal graphene, will be at a low price the technical problem to be solved is that cheap, efficient, magnanimity
The black liquid of value is converted into the single crystal graphene of high added value, high quality, while realizing the controllable of graphene particle size
It is standby.
A kind of method that black liquid prepares single crystal graphene, it is characterised in that this method carries out in accordance with the following steps:
(1) black liquor made from soda pulping process (hydro-thermal 30min at 160 DEG C), is uniformly mixed with isometric deionized water, surpasses
Sound 10min, mixed liquor are placed in the reaction kettle of polytetrafluoroethylliner liner
(2) hydrothermal carbonization: reaction kettle being placed in 180 DEG C of baking ovens and reacts 12h, reaction solution is diluted, and is dialysed surplus to remove
Remaining alkali and other impurity metal ions
(3) size regulates and controls: by adjusting the hydro-thermal reaction time (3,9,12h), it can be achieved that the regulation of graphene size, obtains
For average-size at 0.3-2.5 μm, full-size reaches 5 μm of single crystal graphene.
The present invention has the following advantages and outstanding effects:
(1) it the present invention provides the technology that one kind can convert black liquid to single crystal graphene, realizes cheap, high
Effect, the single crystal graphene for converting the black liquid of low value to magnanimity high added value, high quality, this method can be looked forward to by papermaking
Industry large-scale use.
(2) graphene of the invention by simply regulating and controlling three kinds of sizes that the reaction time obtains, the graphene for reacting 3h are flat
Having a size of 0.36 μm, the graphene average-size for reacting 9h is 0.56 μm, and reaction 12h graphene average-size is 2.5 μm, is led to
The controllable preparation for preparing graphene different-grain diameter can be realized by spending the simple regulation differential responses time.
Detailed description of the invention
Fig. 1 is graphene low power, high power transmission electron microscope photo and Fourier transformation figure prepared by embodiment 1.
Fig. 2 is graphene AFM figure and size, height statistical chart prepared by embodiment 2.
Fig. 3 is the Raman characterization of graphene quantum dot prepared by embodiment 1
Fig. 4 is the XPS characterization of graphene quantum dot prepared by embodiment 1.
Fig. 5 is that graphene prepared by embodiment 1 obtains AFM figure, high power transmission plot and size system under the differential responses time
Meter.
Fig. 6 black liquid prepares the experiment flow figure of graphene
Specific embodiment
Embodiment 1
(1) taking concentration made from soda pulping process (hydro-thermal 30min at 160 DEG C) is black liquor 3.5mL, the deionization with 3.5mL
Water is uniformly mixed, in the reaction kettle of the polytetrafluoroethylliner liner of ultrasonic 10min, 25mL
(2) hydrothermal carbonization: mixed liquor being placed in the polytetrafluoroethylliner liner of 25mL stainless steel cauldron, 180 DEG C of baking ovens
Middle reaction 12h, reaction solution is diluted, and is placed in deionized water mounted in the bag filter of 500 molecular weight and is dialysed 3 days to remove residue
Acid and other impurity metal ions, the solution after dialysis is lyophilized up to graphene.
(3) size regulates and controls: by adjusting the hydro-thermal reaction time (3,9,12h), it can be achieved that the regulation of graphene size, obtains
For average-size at 0.3-2.5 μm, full-size reaches 5 μm of single crystal graphene.
Embodiment 2
Processing method is with example 1, except that then adopting hydro-thermal reaction 3h in 180 DEG C of baking oven is placed in step (2)
It is dialysed with same method, freeze-drying.
Embodiment 3
Processing method is with example 1, except that then adopting hydro-thermal reaction 9h in 180 DEG C of baking oven is placed in step (2)
It is dialysed with same method, freeze-drying.
Embodiment 4
Processing method is with example 1, except that hydro-thermal reaction will be placed in 180 DEG C of baking oven for 24 hours in step (2), then
It is dialysed using same method, freeze-drying.
Embodiment 5
Graphene quantum dot is characterized:
(1) Electronic Speculum characterizes: gained graphene solution deposits in micro-grid, characterizes graphene shape with transmission electron microscope after drying
Looks, partial size and lattice (attached drawing 1a), and graphene particle size and its distribution are counted, there are smooth, partial folds, sheet knot
Structure, partial size are that average-size is 2.5 μm, and graphene is that 1-3 layers of (attached drawing 1b) full-size are 5 μm, lattice 0.21nm, corresponding
Regular hexagonal shaped pattern, which is presented, directly in graphene 1100 crystal face (attached drawing 1c) Fourier transformation figure proves that gained graphene is
Monocrystalline state structure.(attached drawing 2a) is characterized by AFM；Size statistic statistics indicate that (attached drawing 2b) thickness in 1-3 layers of (0.9-
1.4nm)。
(2) Raman is characterized: the intensity ratio at the peak D and the peak G is 0.73 (attached drawing 3), the graphene defect being prepared it is less and
With larger range sp2Hydridization domain.
(3) XPS is characterized: main bonding mode is carbon-carbon double bond (C=C), has less oxygen-containing functional group, such as C-O, C=
O etc. (attached drawing 4).
(4) by simply regulating and controlling the graphene for three kinds of sizes that the reaction time obtains, the graphene average-size of 3h is reacted
It is 0.36 μm, the graphene average-size for reacting 9h is 0.56 μm, and reaction 12h graphene average-size is 2.5 μm, by simple
The regulation differential responses time can realize the controllable preparation (attached drawing 5) for preparing graphene different-grain diameter.
(5) Fig. 6 is the experiment flow figure that preparation is prepared graphene by black liquid.
Claims (9)
1. a kind of method that black liquid prepares high quality single crystal graphene, it is characterised in that pass through the hydro-thermal carbon to black liquid
The high quality single crystal graphene film that average largest dimensions are 2.5 μm can be prepared by changing, and adjust reaction condition, it can be achieved that graphene quantum
The controllable preparation of the particle size of point, this method is simple, cheap, can utilize on a large scale the pollutant waste material of papermaking enterprise, has
There is biggish economic benefit.
2. the graphene of method preparation as described in claim 1, it is characterised in that the black liquid raw material is selected from sulfate
Method, sulphite process, alkaline pulping black liquor, the preferably black liquor of soda pulping process.
3. preparation method as described in claim 1, it is characterised in that this method carries out in accordance with the following steps:
(1) black liquor made from soda pulping process (hydro-thermal 30min at 160 DEG C), is uniformly mixed with isometric deionized water, ultrasound
10min, mixed liquor are placed in the reaction kettle of polytetrafluoroethylliner liner
(2) hydrothermal carbonization: reaction kettle being placed in 180 DEG C of baking ovens and reacts 12h, reaction solution is diluted, and is dialysed remaining to remove
Alkali and other impurity metal ions
(3) size regulates and controls: by adjusting the hydro-thermal reaction time (3,9,12h), it can be achieved that the regulation of graphene size, is put down
For equal size at 0.3-2.5 μm, full-size reaches 5 μm of single crystal graphene.
4. soda pulping process processing method as claimed in claim 3, it is characterised in that the inorganic base is selected from lithium hydroxide, hydrogen
Potassium oxide, sodium hydroxide, preferably sodium hydroxide.
5. nitric acid treatment method as claimed in claim 3, it is characterised in that the processing time be selected from 3h, 6h, 9h, 12h,
For 24 hours, 48h, 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. various sizes of graphene obtained as claimed in claim 3, which is characterized in that different the hydro-thermal reaction time preparations
Graphene there is different sizes, different surfaces state and pore structure, it is smaller by (tens to form size hydrothermal carbonization 3h
To several hundred nanometers), less complete graphene film, surface is sufficiently complete smoothly to have many larger holes, after being reacted to 9h, stone
Black alkene nanometer sheet further polymerize, and forms bigger, more complete graphene film (several hundred nm to 1 μm or so), graphene surface
Between tend to complete and smooth, hole also further becomes smaller, tails off, until reaction 12h when, further polycondensation is formed graphene
The graphene film of several micron-scale sizes, forms that surface is relatively smooth, the graphene of structural integrity, without hole, no
Same size, surface state graphene film to catalysis, absorption etc. different fields be with a wide range of applications.
8. graphene obtained as claimed in claim 3, which is characterized in that the graphene size distribution uniform of preparation, greatly
2.5 μm or so are all concentrated on, thickness directly affects material in 1-3 layers (0.9-1.4nm), the size and the number of plies of graphene sheet layer
Performance.
9. the graphene of method preparation as claimed in claim 3, it is characterised in that its light transmittance is up to 96%, to for electrically conducting transparent
The transparent conductive materials such as electrode have important application value.
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|---|---|---|---|---|
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| CN105217607A (en) * | 2015-08-22 | 2016-01-06 | 苏州正业昌智能科技有限公司 | A kind of graphene preparation method based on xylogen |
| CN105600779A (en) * | 2016-02-23 | 2016-05-25 | 广西科学院 | Method for preparing self-assembly all-carbon three-dimensional graphene from papermaking black liquid |
| CN205419786U (en) * | 2016-02-23 | 2016-08-03 | 广西科学院 | Device with three -dimensional graphene materials of black liquor preparation |
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2018
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| CN105217607A (en) * | 2015-08-22 | 2016-01-06 | 苏州正业昌智能科技有限公司 | A kind of graphene preparation method based on xylogen |
| CN105060289A (en) * | 2015-09-21 | 2015-11-18 | 中南大学 | Method for preparing fewer-layer graphene on basis of biomass waste |
| CN105600779A (en) * | 2016-02-23 | 2016-05-25 | 广西科学院 | Method for preparing self-assembly all-carbon three-dimensional graphene from papermaking black liquid |
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