CN105692581A - Preparation method of high-crystallization graphene quantum dots capable of replacing fullerene - Google Patents
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Abstract
The invention discloses a preparation method of high-crystallization graphene quantum dots capable of replacing fullerene. The preparation method comprises the steps: taking small-molecular carbohydrate as a carbon source, and synthesizing carbon quantum dots with the size of nanoscale by a one-step hydrothermal method; carrying out temperature controlled microwave reduction treatment on the carbon quantum dots, and removing oxygen-containing groups on the surface; mixing a chloroform solvent with a carbon quantum dot aqueous solution after the completion of treatment, carrying out extraction and separation operation on the mixed solution, collecting a lower-layer chloroform solution, and removing the lower-layer chloroform solvent by using a reduced pressure distillation method to obtain the final product. The preparation method has the advantages of easy operation, short time and high yield, and can realize large scale preparation; the graphene quantum dots soluble in an organic phase and uniform in size can be obtained through the one-step solvent selection separation action, and are expected to be applied in light detectors, solar cells and other organic photovoltaic fields.
Description
Technical field
The invention belongs to the preparation field of carbon nanomaterial, more particularly, relate to one and there is sp2The class graphene quantum dot (GQD) of the highly crystalline structure that hydbridized carbon atoms is leading, it can be applied in organic photovoltaic cell as a kind of electron acceptor material substituting fullerene derivate。
Background technology
In the regenerative resources such as solar energy, wind energy, Hydrogen Energy, flo gasifying of coal, the photovoltaic energy converted solar energy into electrical energy is one of following most promising energy。Account for the inorganic solar cell of main flow at present, such as monocrystal silicon, polysilicon solar cell, although energy conversion efficiency (PCE) is higher, but its extensive use of high energy consumption production technology and high price limit。Comparatively speaking, polymer solar battery has light weight, flexible, production cost is low and is easily achieved the unique advantages such as large area processing and has very big potentiality (LiG in extensively utilizing solar energy, ShrotriyaV, YangY, etal., High-efficiencySolutionProcessablePolymerPhotovoltaicCel lsbySelf-organizationofPolymerBlends.Nat.Mater., 2005, 4:864 868.KosterLJA, MihailetchiVD, BlomPWM.UltimateEfficiencyofPolymer/fullereneBulkHeteroj untionSolarCells.Appl.Phys.Lett., 2006, 88:093511.)。In polymer solar battery field, use conjugated polymer as electron donor, fullerene and derivant thereof are as the research direction that the polymer/fullerene solaode (polymer/fullerenesolarcells, PFSCs) of electron acceptor is focus the most。But, as a kind of three-dimensional aromatic with unique cage structure, the preparation of fullerene is generally extremely complex, and typically require it is chemically modified could better realize its application。For this, development of new acceptor material is just likely the preparation of organic photovoltaic cell and provides new approaches。
Carbon is the basis of all known life on the earth. owing to it has various electron orbit characteristic (sp, sp2、sp3), therefore form many structures and the peculiar material of character。At the beginning of 21 century, the scientist of Clemson University of the U.S. develops a kind of Novel Carbon Nanomaterials carbon quantum dot (CQD) first, due to the similarly sized disk stacking at the graphene sheet layer of several nanometers of its structure or ball, also have been reported that and be referred to as " graphene quantum dot " (GQD) (XuX, RayR, GuY, etal., ElectrophoreticAnalysisandPurificationofFluorescentSingl e-WalledCarbonNanotubeFragments, J.Am.Chem.Soc., 2004, 126, 12736-12737.), quickly, the superior function of this material is just subject to people's extensive concern。Further study showed that, GQD has high chemical stability, light stability and special optical property (S.T.Yang, L.Cao, P.G.J.Luo, etal., CarbonDotsforOpticalImaginginVivo, J.Am.Chem.Soc., 2009,131,11308 11309.Z.P.Zhang, J.Zhang, N.Chen, etal., GrapheneQuantumDots:AnEmergingMaterialforEnergy-relatedA pplicationsandBeyond, EnergyEnviron.Sci., 2012,5,8,869 8890)；As " quantum dot " material of a kind of nanoscale, the biocompatibility that it also has particle diameter little (being generally less than 10nm), excitation wavelength is adjustable and excellent。In addition, relative to traditional quantum dot and organic dyestuff, it has again low toxicity, stable, advantage (the Z.A.Qiao such as preparation is easy and is easily chemically modified, Y.F.Wang, Y.Gao, etal., CommerciallyActivatedCarbonastheSourceforProducingMultic olorPhotoluminescentCarbonDotsbyChemicalOxidation, Chem.Commun., 2010, 46, 8812-8814.F.Wang, Z.Xie, H.Zhang, etal., HighlyLuminescentOrganosilane-FunctionalizedCarbonDots, Adv.Funct.Mater., 2011, 21, 1027-1031)。GQD can be divided into oil-soluble carbon point and water-soluble carbon point according to himself whether being dissolved in water。Wherein water solublity GQD surface has the hydrophilic radicals such as substantial amounts of carboxyl, hydroxyl。And research worker is also based on these surface activity sites, carry out extensively and effectively inquiring into (S.N.BakerandG.A.Baker to its potential using value, LuminescentCarbonNanodots:EmergentNanolights, Angew.Chem., Int.Ed., 2010,49,6,726 6744.), they can be organic with multiple, inorganic, biomolecule is compatible and causes extensive concern。In fact; these water solublity oxy radicals would generally inevitably generate in the forming process of GQD and be attached to its surface; so GQD was also considered as once " surface-functionalized carbon point " (carbogenicnanodots) (A.B.Bourlinos, A.Stassinopoulos, D.Anglos; etal.; PhotoluminescentCarbogenicDots, Chem.Mater., 2008; 20,4,539 4541)。But, everything has dual character invariably, these avtive spots are while providing the unlimited possibility in GQD application, also become and limit its restraining factors played in some field: they cause on the one hand the organic facies of GQD poorly soluble, significantly limit the electron transport ability of GQD on the other hand。Therefore, if wanting to develop its quasiconductor application characteristic, in addition it is also necessary to exploring the method that one prepares " purely " GQD, namely surface does not have oxygen-containing defected GQD。
At present, the method about preparation with the relatively GQD of perfect structure also rarely has report, Liu etc. utilize nano-graphite granule (GNPs) as raw material, the method peeled off by low boiling point organic solvent has prepared " zero-fault " pure graphene quantum dot (Oxygen-freepristineGQD) (F.Liu, Min-HoJang, HyunDongHa, etal., FacileSyntheticMethodforPristineGrapheneQuantumDotsandGr apheneOxideQuantumDots:OriginofBlueandGreenLuminescence, Adv.Mater., 2013, 25, 3657 3662)。The GQD that the method obtains is practically free of any oxydant, and most of carbon all presents sp2The type of hydridization。But, the raw material that the method uses, the i.e. pure graphite granule of nanoscale (GNPs), price is sufficiently expensive, and the general only seminar that minority is special just can have, and therefore this method is difficult to accomplish large-scale production。
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that the preparation method that what a kind of organic facies was solvable have the GQD of ad hoc structure: obtained product has sp2The high crystalline structure that hydbridized carbon atoms is leading, this structure is so as to possessed π-pi-conjugated " passage " realizing photoelectron transfer just, so that its quantity of photogenerated charge transmittability is far above the CQD prepared by conventional method；Simultaneously as this product surface oxygen-containing functional group defect is few, so it has the characteristic of hydrophobic oleophilic oil (organic solvent), provide basis for its application in organic photovoltaic devices further。The preparation process of whole material is not related to any toxic reagent and complicated apparatus, and on the contrary, the method has that technique is simple to operation, the extensive cost of raw material sources is low, product whole productivity relatively advantages of higher, is suitable for large-scale production。
The technical purpose of the present invention is achieved by following technical proposals:
The preparation method of the high crystalline class graphene quantum dot of alternative fullerene, carries out as steps described below:
Step 1, by the concentrated sulphuric acid ultrasonic disperse of the aqueous solution of glycerol that volume fraction is 70% and mass percent 98% uniformly after, room temperature is naturally cooled to after sealed environment is warmed up to 160-220 DEG C of reaction 12-24h, the brown solution of generation is poured out, being filtered to remove solid impurity therein and surplus solution part carries out dialysis purification operations, after purification, gained solution is designated as A；
In step 1, the aqueous solution of described glycerol and the volume ratio of concentrated sulphuric acid are (10,000 5000): (10 50)。
Step 2, anhydrous N by solution A and 5 times of solution A volumes, dinethylformamide solvent carry out mixing and ultrasonic disperse uniformly after carry out microwave heating, suspension is taken out and reduces pressure after end and residual solvent is distilled off, solute partially adds 50-200mL ultra-pure water dissolved dilution, and diluent is designated as solution B；
In step 2, described microwave heating power is 600-800W, and under N2 protective condition, microwave reduction processes 1-8min。
Step 3, by solution B ultrasonic disperse uniformly after pour in separatory funnel and add isopyknic chloroform, stirring, so that both mix homogeneously, stands mixed liquor to forming obvious layering interfaces, collects lower floor's chloroformic solution, be designated as solution C；
In step 3, described solution B volume is 50 200mL。
Step 4, rotates evaporation by solution C and eliminates solvent chloroform, obtains end product and high crystalline class graphene quantum dot；
In step 4, use Rotary Evaporators to be operated, after completing, flask is inserted in vacuum drying oven, dry 48～72h under-0.1Mpa vacuum and 60 DEG C of conditions。
Technical scheme utilizes little molecular carbon hydrate to carry out one step hydro thermal method synthesis as carbon source and is of a size of the CQD of several nanometers, these CQD carries out temperature control microwave reduction process, removes the oxy radical on its surface。Followed by the feature of the target GQD hydrophobic oleophilic oil having, by chloroform solvent be disposed after CQD aqueous solution mix, mixed liquor is carried out the operation of extract and separate, collects the chloroformic solution of lower floor。Utilize distillation under vacuum to remove lower floor's chloroform solvent and namely obtain final products, i.e. sp2The highly crystalline GQD that hydbridized carbon atoms is leading。
It is utilized respectively PERKINELMZR company of U.S. PHI1600 type XPS instrument, BRUKER company of Germany Dimension3100 type AFM instrument, the quantum dot of preparation is characterized as below by Jeol Ltd. JEM-2100F type TEM: the distribution of (1) product quantum dot height is homogeneous, without any agglomeration, it is 2-4nm highly substantially, every layer of carbon nanometer disc height is 0.8 1nm, and the actual layer number of product quantum dot is the carbon nanometer disc structure of 25 layers；(2) distribution of sizes of GQD is also more uniform, and the diameter of single GQD is approximately 3-5nm；(3) in GQD, most carbon atoms are sp2Hydridization type, it accounts for whole carbon distribution 90.92% by analysis, and oxygen-containing carbon peak only accounts for less than 10%, is almost negligible。This sign proves: GQD has sp2Oxygen-containing defected few high crystalline structure that hydbridized carbon atoms is leading, i.e. sp2Hydbridized carbon atoms accounts for the 90% of whole carbon。
The method that technical scheme is reduced by microwave combustion method, little for carbon source molecule is carried out drastic reduction by assembling the CQD of formation under hydrothermal conditions from bottom to top, remove the oxy radical of its surface attachment, thus obtain that a kind of organic facies is solvable, it is oxygen-containing defected to be practically free of, main by sp2The GQD product of the highly crystalline structure that the carbon atom of hydridization type is constituted。It is extracted into organic solvent by the characteristic followed by above-mentioned target product hydrophobic oleophilic oil from aqueous dispersions。Develop a kind of method that CQD head product to a large amount of complicated components carries out reduction deoxygenation extract and separate, it is achieved that the high-carbon content of target product, highly crystalline structure。The method raw material sources scope is wide, simple to operate, can complete in the short time, and preparation condition is not all had particular/special requirement by any step related to, it is possible to achieve prepare on a large scale。
Accompanying drawing explanation
Fig. 1 is the AFM figure of GQD prepared by the present invention。
Fig. 2 is the TEM figure of GQD prepared by the present invention。
Fig. 3 is the high-resolution XPS C1s collection of illustrative plates of GQD prepared by the present invention。
Detailed description of the invention
Three embodiments of the present invention are given below, are further illustrating the present invention, rather than restriction the scope of the present invention。
Embodiment 1:
15 μ L concentrated sulphuric acids are added in the aqueous solution of the glycerol that 15mL volume fraction is 70% as ionic catalyst, by ultrasonic for this mixed solution 3 minutes so as to insert in politef hydrothermal reaction kettle after being uniformly dispersed, after building sealing, reactor is put in Muffle furnace, be warmed up to 180 DEG C of reaction 16h。After completion of the reaction, question response still is cooled to room temperature, is poured out the brown solution generated in reactor, is filtered to remove solid impurity therein and surplus solution part carries out dialysis purification operations。The dry DMF solvent of gained solution and 5 times of volumes after purifying is carried out mixing and ultrasonic disperse is uniform, after insert in chemistry microwave reactor, arranging heating power is 600W, microwave reduction process 2min under N2 protective condition。Suspension is taken out and reduces pressure after end and residual solvent is distilled off, solute is partially added 100mL ultra-pure water dissolved dilution, diluent ultrasonic disperse uniformly after pour in separatory funnel, be then poured into isopyknic chloroform, rock, stir and make the two mix homogeneously。Stand mixed liquor 5min obvious layering interfaces to be formed。Collect lower floor's chloroformic solution and add it in round-bottomed flask, Rotary Evaporators is used to eliminate its chloroform solvent, after completing, flask is inserted in vacuum drying oven, dry 48h under-0.1Mpa vacuum and 60 DEG C of conditions, obtain end product and the solvable highly crystalline GQD sample of organic facies。
Embodiment 2:
30 μ L concentrated sulphuric acids are added in the aqueous solution of the glycerol that 30mL volume fraction is 70% as ionic catalyst, by ultrasonic for this mixed solution 4 minutes so as to insert in politef hydrothermal reaction kettle after being uniformly dispersed, after building sealing, reactor is put in Muffle furnace, be warmed up to 200 DEG C of reaction 20h。After completion of the reaction, question response still is cooled to room temperature, is poured out the brown solution generated in reactor, is filtered to remove solid impurity therein and surplus solution part carries out dialysis purification operations。The dry DMF solvent of gained solution and 5 times of volumes after purifying is carried out mixing and ultrasonic disperse is uniform, after insert in chemistry microwave reactor, arranging heating power is 720W, microwave reduction process 3min under N2 protective condition。Suspension is taken out and reduces pressure after end and residual solvent is distilled off, solute is partially added 150mL ultra-pure water dissolved dilution, diluent ultrasonic disperse uniformly after pour in separatory funnel, be then poured into isopyknic chloroform, rock, stir and make the two mix homogeneously。Stand mixed liquor 6min obvious layering interfaces to be formed。Collect lower floor's chloroformic solution and add it in round-bottomed flask, Rotary Evaporators is used to eliminate its chloroform solvent, after completing, flask is inserted in vacuum drying oven, dry 72h under-0.1Mpa vacuum and 60 DEG C of conditions, obtain end product and the solvable highly crystalline GQD sample of organic facies。
Embodiment 3:
40 μ L concentrated sulphuric acids are added in the aqueous solution of the glycerol that 40mL volume fraction is 70% as ionic catalyst, by ultrasonic for this mixed solution 5 minutes so as to insert in politef hydrothermal reaction kettle after being uniformly dispersed, after building sealing, reactor is put in Muffle furnace, be warmed up to 220 DEG C of reaction 24h。After completion of the reaction, question response still is cooled to room temperature, is poured out the brown solution generated in reactor, is filtered to remove solid impurity therein and surplus solution part carries out dialysis purification operations。The dry DMF solvent of gained solution and 5 times of volumes after purifying is carried out mixing and ultrasonic disperse is uniform, after insert in chemical microwave reactor, arranging heating power is 800W, at N2Under protective condition, microwave reduction processes 5min。Suspension is taken out and reduces pressure after end and residual solvent is distilled off, solute is partially added 200mL ultra-pure water dissolved dilution, diluent ultrasonic disperse uniformly after pour in separatory funnel, be then poured into isopyknic chloroform, rock, stir and make the two mix homogeneously。Stand mixed liquor 7min obvious layering interfaces to be formed。Collect lower floor's chloroformic solution and add it in round-bottomed flask, Rotary Evaporators is used to eliminate its chloroform solvent, after completing, flask is inserted in vacuum drying oven, dry 72h under-0.1Mpa vacuum and 60 DEG C of conditions, obtain end product and the solvable highly crystalline GQD sample of organic facies。
Above the present invention has been done exemplary description; should be noted that; when without departing from the core of the present invention, any simple deformation, amendment or other those skilled in the art can not spend the equivalent replacement of creative work to each fall within protection scope of the present invention。
Claims (4)
1. the preparation method of the high crystalline class graphene quantum dot of alternative fullerene, it is characterised in that carry out as steps described below:
Step 1, by the concentrated sulphuric acid ultrasonic disperse of the aqueous solution of glycerol that volume fraction is 70% and mass percent 98% uniformly after, room temperature is naturally cooled to after sealed environment is warmed up to 160-220 DEG C of reaction 12-24h, the brown solution of generation is poured out, being filtered to remove solid impurity therein and surplus solution part carries out dialysis purification operations, after purification, gained solution is designated as A；In step 1, the aqueous solution of described glycerol and the volume ratio of concentrated sulphuric acid are (10,000 5000): (10 50)；
Step 2, anhydrous N by solution A and 5 times of solution A volumes, dinethylformamide solvent carry out mixing and ultrasonic disperse uniformly after carry out microwave heating, suspension is taken out and reduces pressure after end and residual solvent is distilled off, solute partially adds 50-200mL ultra-pure water dissolved dilution, and diluent is designated as solution B；
Step 3, by solution B ultrasonic disperse uniformly after pour in separatory funnel and add isopyknic chloroform, stirring, so that both mix homogeneously, stands mixed liquor to forming obvious layering interfaces, collects lower floor's chloroformic solution, be designated as solution C；
Step 4, rotates evaporation by solution C and eliminates solvent chloroform, obtains end product and high crystalline class graphene quantum dot。
2. the preparation method of the high crystalline class graphene quantum dot of alternative fullerene according to claim 1, it is characterised in that in step 2, described microwave heating power is 600-800W, at N2Under protective condition, microwave reduction processes 1-8min。
3. the preparation method of the high crystalline class graphene quantum dot of alternative fullerene according to claim 1, it is characterised in that in step 3, described solution B volume is 50 200mL。
4. the preparation method of the high crystalline class graphene quantum dot of alternative fullerene according to claim 1, it is characterized in that, in step 4, use Rotary Evaporators to be operated, after completing, flask is inserted in vacuum drying oven, dry 48～72h under-0.1Mpa vacuum and 60 DEG C of conditions。
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