CN106573778A - Bandgap engineering of carbon quantum dots - Google Patents
Bandgap engineering of carbon quantum dots Download PDFInfo
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- CN106573778A CN106573778A CN201580044351.5A CN201580044351A CN106573778A CN 106573778 A CN106573778 A CN 106573778A CN 201580044351 A CN201580044351 A CN 201580044351A CN 106573778 A CN106573778 A CN 106573778A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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Abstract
Embodiments of the present disclosure pertain to scalable methods of producing carbon quantum dots with desired bandgaps by the following steps: exposing a carbon source to an oxidant at a reaction temperature, where the exposing results in the formation of the carbon quantum dots; and selecting a desired size of the formed carbon quantum dots. In some embodiments, the selecting occurs by at least one of separating the desired size of the formed carbon quantum dots from other formed carbon quantum dots; selecting the reaction temperature that produces the desired size of the formed carbon quantum dots; and combinations of such steps. The desired size of carbon quantum dots can include a size range. The methods of the present disclosure can also include a step of purifying the formed carbon quantum dots prior to selecting a desired size.
Description
Cross reference to related applications
This application claims the priority of the U.S. Provisional Patent Application the 62/014,627th of the submission of on June 19th, 2014.
Additionally, the application is related to the International Patent Application No. PCT/US2014/036604 of the submission of on May 2nd, 2014, it requires 2013
The priority of the U.S. Provisional Patent Application the 61/818,800th that on May 2, in submits to.The complete content of above-mentioned per part of application leads to
Cross and be incorporated by reference into herein.
The statement of relevant federal funding research
The present invention complete under governmental support, grant number be FA9550-09-1-0581 and FA9550-14-1-0111, two
Person is authorized by U.S. Department of Defense.Government has certain rights to this invention.
Background
The method of the carbon quantum dot with particular bandgap is currently formed in cost, efficiency, reaction condition and amplification scale etc.
There are many restrictions in aspect.Accordingly, it would be desirable to more effective way is preparing the carbon quantum dot with required band gap.
General introduction
In some embodiments, present disclosure is related to prepare the amplified scale of the carbon quantum dot with required band gap
Method.In some embodiments, disclosed method include make carbon source at the reaction temperatures catalytic oxidation agent the step of, its
Described in contact result be to form carbon quantum dot.Disclosed method also includes selecting the carbon quantum for being formed of required size
The step of point.
In some embodiments, the required size of carbon quantum dot includes a size range.In some embodiments,
The required size of carbon quantum dot in the range of about 1-200nm diameters, in the range of about 1-100nm diameters, or about 2-80nm
In the range of diameter.
In some embodiments, the selection of quantum dot size is carried out by selecting reaction temperature, and the reaction temperature is produced
The required size of the formed carbon quantum dot of life.In some embodiments, selected reaction temperature is during contact procedure
Keep constant design temperature.In some embodiments, selected reaction temperature be during contact procedure gradually increase or
The thermograde of reduction.In some embodiments, the scope of selected reaction temperature is about 25-200 DEG C, about 50-150 DEG C, or
About 100-150 DEG C of person.In some embodiments, the required size of carbon quantum dot reduces as selected reaction temperature increases.
In some embodiments, the selection of carbon quantum dot size is by by the carbon quantum for being formed with required size
Point separates to carry out with the carbon quantum dot that other are formed.In some embodiments, separate is carried out by filtration, such as slipstream
Ultrafiltration.In some embodiments, filtration passes sequentially through multiple perforated membranes with different hole sizes is carried out.In some embodiment party
In formula, separate is carried out by dialysis or repetition dialysis.
In some embodiments, the carbon source for preparing carbon quantum dot includes but is not limited to coal, coke, graphite, carbon and receives
Mitron, activated carbon, carbon black, fullerene and combinations thereof.In some embodiments, the oxidant for contacting with carbon source includes acid, such as
Sulfuric acid, nitric acid and combinations thereof.
In some embodiments, the step of disclosed method also includes purifying formed carbon quantum dot.At some
In embodiment, purification step including but not limited to extraction, filtration, evaporation, precipitation, dialysis and combinations thereof.
In some embodiments, disclosed method also includes the step of the quantum yield of the carbon quantum dot for improving formed
Suddenly.In some embodiments, it is described improve by hydro-thermal process carbon quantum dot, with one or more alkali process carbon quantum dot,
Process carbon quantum dot, use one or more with one or more hydroxide treatment carbon quantum dot, with one or more dopant
Reducing agent processes carbon quantum dot and combinations thereof to carry out.
Disclosed method can be used to produce various types of carbon quantum dots with various required band gap.In some enforcements
In mode, the carbon quantum dot for being formed includes graphene quantum dot.In some embodiments, the carbon quantum dot for being formed has
Crystallization hexagonal structure.In some embodiments, the carbon quantum dot for being formed is luminescence generated by light.In some embodiments,
The carbon quantum dot for being formed is functionalized with multiple functional groups.In some embodiments, the carbon quantum dot for being formed is Jing
Cross edge functionalization.
Disclosed method may further be used to produce carbon quantum dot in the way of it can amplify scale.For example, in some embodiment party
In formula, disclosed method forms carbon quantum dot with the various high-volume of about 1g carbon quantum dots to about 10 tons of carbon quantum dots.
Description of the drawings
Fig. 1 provides the schematic diagram of the method that the carbon quantum dot (CQD) with required band gap is prepared by size Selection.
Fig. 2 related to the production of graphene quantum dot (GQD) and size separation diagram and data.Fig. 2A is GQD synthesis
Schematic diagram.Fig. 2 B are the schematic diagrames that GQD is separated with cross-flow ultrafiltration.Also show the transmission electron microscope of detached GQD
(TEM) image, including GQDs-S4.5 (Fig. 2 C), GQDs-S16 (Fig. 2 D), GQDs-S41 (Fig. 2 E) and GQDs-S70 (Fig. 2 F).
Fig. 2 G summarize the GQDs-S4.5 measured by TEM, the Size Distribution of GQDs-S16, GQDs-S41 and GQDs-S70.
Fig. 3 provides the Hydrodynamic diameter of the various sizes of GQD obtained by dynamic light scattering (DLS).List figure
Exemplify, to be consistent with the legend of TEM in Fig. 2 G.But, the average-size of DLS physical records is respectively 10 ± 2.5,
27 ± 7.9,41 ± 11 and 76 ± 18nm.
Fig. 4 provides GQDs-S4.5, and GQDs-S16, GQDs-S41 and GQDs-S70's is direct13C pulses evil spirit angle self-rotating nuclear
Magnetic resonance (MAS NMR) (Fig. 4 A) and cross polarization13C MAS NMR (Fig. 4 B) collection of illustrative plates.
Fig. 5 provides the various data of the GQD of synthesis.Fig. 5 A provide GQDs-S4.5, GQDs-S16, GQDs-S41 and
The x-ray photoelectron power spectrum (XPS) of GQDs-S70 is composed entirely, using Au as reference.Also show GQDs-S4.5 (Fig. 5 B), GQDs-
The C1s high-resolution XPS spectrums of S16 (Fig. 5 C), GQDs-S41 (Fig. 5 D) and GQDs-S70 (Fig. 5 E).Fig. 5 F are summarized from figure
The element percentage composition of the different functional groups of 5B-5E.
Fig. 6 provides GQDs-S4.5 (Fig. 6 A), GQDs-S16 (Fig. 6 B), GQDs-S41 (Fig. 6 C) and GQDs-S70 (figure
Solid-state Fourier transform infrared (FTIR) spectrum 6D).
Fig. 7 provides GQDs-S4.5, the UV-Vis absorption spectras of GQDs-S16, GQDs-S41 and GQDs-S70.
Fig. 8 provides GQDs-S4.5 (Fig. 8 A), GQDs-S16 (Fig. 8 B), GQDs-S41 (Fig. 8 C) and GQDs-S70 (figure
Two-dimentional excitation-emission contour map 8D), with about 80mg/L measure in the water that pH is 6.Fig. 8 E are returning for Fig. 8 A-D
One changes intensity chi.Fig. 8 F are the GQD solution in the case where 365nm excites UV lamp.GQDs- is respectively provided with bottle from left to right
The solution of S4.5, GQDs-S16, GQDs-S41 and GQDs-S70.Fig. 8 G compare optical band gap and GQD sizes (from TEM) or
The relation between membrane pore size used in ultrafiltration.
Fig. 9 provides GQDs-S4.5 in NaOH or Na2The comparison of the luminescence generated by light before and after S process.
Figure 10 provides GQDs-T150-7.6 (Figure 10 A), GQDs-T130-25 (Figure 10 B), GQDs-T110-27 (figure
10C) with the C1s high-resolution XPS spectrums of GQDs-T50-54 (Figure 10 D).Figure 10 E summarize the different functional groups from Figure 10 A-D
Element percentage composition.
Figure 11 provides the TEM image of the GQD for synthesizing at different temperatures, including GQDs-T150-7.6 (Figure 11 A),
GQDs-T130-25 (Figure 11 B), GQDs-T110-27 (Figure 11 C) and GQDs-T50-54 (Figure 11 D).Correspondence from TEM is average
Diameter is respectively 7.6 ± 1.8,25 ± 5.0,27 ± 3.8 and 54 ± 7.2nm.Figure 11 E summarize the GQD's from Figure 11 A-11D
Size Distribution.
Figure 12 provides the substance assistant laser desorpted/MALDI-MS (MALDI-MS) of the GQD for synthesizing at different temperatures.
As synthesis temperature is increased to 150 DEG C from 50 DEG C, the average diameter of GQD is 54 ± 7.2,27 ± 3.8,25 ± 5.0 and 7.6 ±
1.8nm () in figure from top to bottom.The corresponding molecular weight at GQD peaks is respectively 60,49,44 and 27kD.
Figure 13 provides the composite diagram of Fig. 2 G and 9E.GQDs-T100-35 is by GQDs-S4.5, GQDs-S16, GQDs-S41
With GQDs-S70 compositions.The all GQD for relatively synthesizing under different temperatures, GQDs-T100-35 is comprising size in 4.5nm and 80nm
Between particulate, but quantity is few.Main trend is that, as temperature is raised, main peak to small diameter offsets.
Figure 14 provides GQDs-T50-54, and GQDs-T110-27, GQDs-T130-25 and GQDs-T150-7.6's is direct13C pulse MAS NMR (Figure 14 A) and cross polarization13C MAS H NMR spectroscopies (Figure 14 B).GQD-T110-27 cross polarization spectrum because
Aliphatic impurity and show enhancing.
Figure 15 provides GQDs-T150-7.6, the UV- of GQDs-T130-25, GQDs-T110-27 and GQDs-T50-54
Vis absorption spectras.
Figure 16 provides GQDs-T150-7.6 (Figure 16 A), GQDs-T130-25 (Figure 16 B), GQDs-T110-27 (figure
16C) with the two-dimentional excitation-emission contour map of GQDs-T50-54 (Figure 16 D).Figure 16 E show normalization engineer's scale.Concentration
It is about 30mg/L, pH is about 6.Figure 16 F provide the GQD solution in the case where 365nm excites UV lamp.Solution from left to right is
GQDs-T150-7.6, GQDs-T130-25, GQDs-T110-27 and GQDs-T50-54.Figure 16 G summarize in Figure 16 A-D
Peak intensity under 300nm and 320nm excitation wavelengths.
Figure 17 provides the emission spectra (exciting under 345nm) in 120 DEG C of GQD synthesized by bituminous coal.Illustration shows
GQD solution under 365nm UV lamps.
Figure 18 shows the emission spectra of the GQD for synthesizing 1 hour and 6 hours at 130 DEG C.The spectrum is at 325nm (Figure 18 A)
With excite under 365nm (Figure 18 B).
Figure 19 provides FTIR (Figure 19 A), Raman (Figure 19 B) and XRD (Figure 19 C) spectrums of anthracite and graphite.In Raman
In spectrum, anthracite is in 1350cm-1The larger D peaks at place represent higher defect.In XRD spectrums, the crystal face of anthracite and graphite
Spacing (d-spacing) is respectively 0.346nm and 0.337nm.Anthracite represents less domain at about 26 ° of broader peak.
Describe in detail
It should be appreciated that overall description and detailed description below above is all illustrative and explanatory, not to requiring
The theme of protection is construed as limiting.In this application, the use of singulative includes plural form, word " one " or " one kind " table
Show " at least one/a kind of ", the use of "or" refers to "and/or", unless otherwise expressly specified.Additionally, word " including " and its
His form such as "comprising", the use of " containing " are not restricted.In addition, such as " element " or word as " component " are covered
Element comprising a unit or component and element or component comprising more than one unit, unless otherwise expressly specified.
Each section header used herein is, for the purpose of tissue, to should not be construed as limiting the theme.Quote in the application
All Files or file part, including but not limited to patent, patent application, article, books and paper, all explicitly by ginseng
Examine and be hereby incorporated by with its complete content, for any purpose.Defined in one or more documents and similar material for being combined
Term and the application in it is competing to the definition of the term in the case of, be defined by the application.
By by electron confinement in zero dimension (0-D) or one-dimensional (1-D) nanostructured come to inorganic nano rod and quantum dot
Be adjusted having attracted substantial amounts of research interest, and extensively application found in many fields, such as photovoltaic device, biologic medical and
Bio-imaging, and as light emitting source.Adjusting the conventional method of the band structure of these materials includes many approach, such as In2O3Receive
The laser molecular beam epitaxy growth on rice island, the Supramolecular Assembling of golden nanometer particle, compression shell (compressive shell) exists
Epitaxial deposition in CdTe quantum, the plasma enhanced chemical vapor deposition of silicon quantum dot, and MoS2The strain control of layer
System.But, such method needs the specific apparatus being not readily available or strict reaction condition.Moreover, it is such
Method generally takes high.Additionally, the inorganic-quantum-dot produced with such method typically has toxicity.Therefore, inorganic quantum
The application of point is still restricted.
Although the inorganic-quantum-dot for studying for a long period of time often has more sharp transmitting, the carbon-based quantum dot (CQD) that lights has
Shi Qi high-biocompatibilities aspect shows excellent performance, while keeping light to stablize.CQD is verified with minimum poison
Property.Additionally, the preparation method of the CQD with particular bandgap is developed.For example, have been developed for producing by the following means
The method of the CQD with particular bandgap：Using the chromatogram with different eluent gradients wash-outs, with amine cutting and crushing graphite, with
And element doping is carried out to the CQD of initial preparation.However, the synthesis of the isolation technics of complexity, multistep or high reagent cost are limited
The amplification large-scale production of the CQD with required band gap.Accordingly, it would be desirable to the improved method for producing the CQD with required band gap.This
The various embodiments of disclosure meet this demand.
In some embodiments, this disclosure provides production with required band gap carbon quantum dot can multiplying gauge
The method of mould.In some embodiments, as shown in figure 1, disclosed method includes：Carbon source is set to contact oxygen at the reaction temperatures
Agent (step 10), wherein the result of the contact is to form carbon quantum dot (step 12).In some embodiments, the disclosure
Method the step of also include purifying formed carbon quantum dot (step 14).In some embodiments, disclosed method
The step of also including the required size of selection formed carbon quantum dot (step 16).In some embodiments, carbon quantum dot
The selection of size with the carbon quantum dot that other are formed by the carbon quantum dot for being formed with required size by separating (step
18), reaction temperature is selected to enter to produce the required size (step 20) of formed carbon quantum dot or the combination of these steps
OK.
As described herein, make various carbon sources that various oxidants are contacted under various reaction temperatures using various methods,
So as to form the carbon quantum dot of various quantity and type.Additionally, the institute of the carbon quantum dot formed using various method choices
Need size.
Oxidant
Carbon quantum dot is formed using various oxidants.In some embodiments, oxidant includes acid.In some enforcements
In mode, acid includes but is not limited to sulfuric acid, nitric acid, phosphoric acid, hypophosphorous acid, oleum (fuming sulfuric acid), salt
Sulfur trioxide, chlorosulfonic acid in acid, pyrosulfuric acid (oleum), sulfuric acid and combinations thereof.
In some embodiments, the oxidant for forming carbon quantum dot is the mixture of sulfuric acid and nitric acid.At some
In embodiment, oxidant is nitric acid.In some embodiments, oxidant is only made up of nitric acid.In some embodiments,
Oxidant includes but is not limited to potassium permanganate, sodium permanganate, sodium nitrate, hypophosphorous acid, nitric acid, sulfuric acid, hydrogen peroxide and combinations thereof.
In some embodiments, oxidant is the mixture of potassium permanganate, sulfuric acid and hypophosphorous acid.In some embodiments, aoxidize
Agent includes 20% oleum.In some embodiments, oxidant includes 98% sulfuric acid.In some embodiments,
Oxidant is the combination of sodium nitrate and nitric acid.The use of other oxidants is also foreseeable.
Carbon source
Disclosed method can form carbon quantum dot using polytype carbon source.For example, in some embodiments,
Carbon source includes but is not limited to coal, coke, graphite, CNT, activated carbon, carbon black, fullerene and combinations thereof.
In some embodiments, carbon source includes coal.Various types of coals can be used as carbon source to form carbon quantum dot.Example
Such as, in some embodiments, coal includes but is not limited to anthracite, bituminous coal, ub-bituminous coal, grade metamorphic bituminous, asphaltene, pitch, mud
Coal, brown coal, thermal coal, petrochemical industry oil (petrifiedoil) and combinations thereof.In some embodiments, carbon source includes anthracite.
In some embodiments, carbon source includes bituminous coal.Other coals are also predictable as the use of carbon source.
In some embodiments, carbon source includes coke.In some embodiments, coke is obtained by pitch.At some
In embodiment, coke is obtained by bituminous coal.In some embodiments, coke is obtained by pitch and bituminous coal.In some embodiment party
In formula, carbon source is the combination of coke and coal.The use of other carbon sources is also predictable.
Carbon source catalytic oxidation agent
Carbon source catalytic oxidation agent is made using various methods.In some embodiments, the contact occurs comprising oxygen
In the solution of agent.In some embodiments, the contact is included in the presence of oxidant and carries out sonicated to carbon source.
In some embodiments, the contact is included in the presence of oxidant and carbon source is stirred.In some embodiments,
The contact is included in the presence of oxidant, and carbon source is heated at the reaction temperatures.In some embodiments, react
Temperature is at least about 100 DEG C.In some embodiments, the scope of reaction temperature is about 100-150 DEG C.
Carbon source can durations different from oxidising agent.For example, in some embodiments, the contact occurs about 1 minute
To about 48 hours.In some embodiments, the contact occurs about 1 hour to about 24 hours.In some embodiments, institute
State contact to occur about 15 hours to about 24 hours.
In some embodiments, two or more oxidants can be made to contact carbon source successively.For example, in some embodiment party
In formula, the first oxidant mixes with carbon source.Then, the second oxidant mixes with carbon source.In some embodiments, the first oxidation
Agent is sulfuric acid, and the second oxidant is nitric acid.
In some embodiments, single-oxidizer is made to contact with carbon source.In some embodiments, single-oxidizer is
Nitric acid.The additive method for making carbon source catalytic oxidation agent is also predictable.
The carbon quantum dot of formation
Disclosed method can be used to form polytype carbon quantum dot.The other embodiment of the disclosure is related to institute's shape
Into carbon quantum dot.
In some embodiments, the carbon quantum dot of the disclosure is in primitive form.In some embodiments, the disclosure
Carbon quantum dot be in unfunctionalized form.In some embodiments, the carbon quantum dot of the disclosure is with multiple functional group's senses
Change.In some embodiments, functional group include but is not limited to amorphous carbon, epoxide, carbonyl, carboxyl, aryl, alkyl, thiazolinyl,
Ketone group, ester, amine, acid amides and combinations thereof.
In some embodiments, the carbon quantum dot of the disclosure carries out edge functionalization with multiple functional groups.In some realities
In applying mode, the carbon quantum dot of the disclosure includes the oxygen additives on its edge.In some embodiments, the carbon amounts of the disclosure
Son point includes the amorphous carbon additives on its edge.In some embodiments, the carbon quantum dot of the disclosure includes Graphene
Quantum dot.
The carbon quantum dot of the disclosure may include the layer of various quantity.For example, in some embodiments, the carbon amounts of the disclosure
Son point has individual layer.In some embodiments, the carbon quantum dot of the disclosure has multiple layers.In some embodiments, originally
Disclosed carbon quantum dot has about 2 layers to about 4 layers.
The carbon quantum dot of the disclosure may include various structures.For example, in some embodiments, the carbon quantum dot of the disclosure
With crystallization hexagonal structure.
The carbon quantum dot of the disclosure can also have various properties.For example, in some embodiments, the carbon quantum of the disclosure
Point is luminescence generated by light.In some embodiments, the carbon quantum dot of the disclosure is luminous from human eye visible range.In some realities
In applying mode, the carbon quantum dot of the disclosure lights from bluish-green (2.9eV) of human eye visible spectrum to orange red (2.05eV) region.
The carbon quantum dot of the disclosure can also have various molecular weights.For example, in some embodiments, the carbon amounts of the disclosure
Son molecular weight of the point with about 20kD to about 100kD scopes.In some embodiments, the carbon quantum dot of the disclosure has about
The molecular weight of 25kD to about 75kD scopes.In some embodiments, the carbon quantum dot of the disclosure has about 40kD to about 60kD
The molecular weight of scope.In some embodiments, the carbon quantum dot of the disclosure has the molecular weight of about 60kD.
The carbon quantum dot of the disclosure can also have sizes.For example, in some embodiments, the carbon quantum of the disclosure
Size of the point including about 1nm diameters to about 200nm diameter ranges.In some embodiments, the carbon quantum dot of the disclosure includes
The size of about 2nm diameters to about 80nm diameter ranges.In some embodiments, the carbon quantum dot of the disclosure includes that about 2nm is straight
The size in footpath to about 65nm diameter ranges.
The carbon quantum dot of the disclosure can also have various quantum yields.For example, in some embodiments, carbon quantum dot
Quantum yield is less than 1% and more than 0.1%.In some embodiments, the quantum yield of carbon quantum dot 1% and 10% it
Between.In some embodiments, the quantum yield of carbon quantum dot can be up to 50%.In some embodiments, carbon quantum dot
Quantum yield can close 100%.
Carbon quantum dot size needed for selecting
Disclosed method may also include the one or more steps of the required size for selecting carbon quantum dot.In some enforcements
In mode, required size includes size range.In some embodiments, required size includes narrow dimension scope.In some realities
In applying mode, required size includes multiple sizes.In some embodiments, the required size of carbon quantum dot includes following scope
Diameter：About 55-85nm, about 45-65nm, about 30-50nm, about 20-35nm, about 20-30nm, about 10-20nm, about 5-10nm,
About 2-6nm, about 2-4nm, or about 1-3nm.
The required size of the carbon quantum dot that the present invention can be formed using various method choices.For example, in some embodiment party
At least one of in formula, the selection is comprised the following steps：By the carbon quantum dot for being formed with required size and other
The carbon quantum dot for being formed is separated；Reaction temperature is selected, to produce the required size of formed carbon quantum dot；And these steps
Rapid combination.
Temperature is selected
In some embodiments, the required size of carbon quantum dot is by selecting reaction temperature to select, and the reaction is warm
Degree produces the required size of formed carbon quantum dot.In some embodiments, selected reaction temperature is in contact procedure mistake
Constant design temperature is kept in journey.In some embodiments, selected reaction temperature is thermograde.For example, in some realities
In applying mode, thermograde gradually increases during contact procedure.In some embodiments, thermograde is in contact procedure
During be gradually reduced.
In some embodiments, selected reaction temperature is in the range of about 25-200 DEG C.In some embodiments, institute
Reaction temperature is selected in the range of about 50-150 DEG C.In some embodiments, model of the selected reaction temperature at about 100-150 DEG C
In enclosing.
In some embodiments, the required size of carbon quantum dot reduces as reaction temperature increases.For example, at some
In embodiment, when selected reaction temperature is about 50 DEG C, selected reaction temperature produces carbon amounts of the diameter in about 45-65nm scopes
Sub- point.In some embodiments, when selected reaction temperature is about 110 DEG C, selected reaction temperature produces diameter in about 20-
The carbon quantum dot of 35nm scopes.In some embodiments, when selected reaction temperature is about 130 DEG C, selected reaction temperature is produced
Carbon quantum dot of the raw diameter in about 20-30nm scopes.In some embodiments, when selected reaction temperature is about 150 DEG C, institute
Reaction temperature is selected to produce carbon quantum dot of the diameter in about 5-10nm scopes.
In some embodiments, the functionalization level of carbon quantum dot increases as selected reaction temperature increases.For example,
In some embodiments, the degree of oxidation of carbon quantum dot increases as reaction temperature increases.In some embodiments, carbon
The band gap of quantum dot increases as selected reaction temperature increases.
Separate
In some embodiments, the required size of carbon quantum dot is by by the carbon quantum for being formed with required size
Point separates to be selected with the carbon quantum dot that other are formed.As described herein, various separation methods can be adopted.
In some embodiments, separate is carried out by filtration.In some embodiments, filter including but not limited to thick
The combination of filter, micro-filtration, ultrafiltration, tangential flow filtration, cross-flow ultrafiltration, dialysis, membrane filtration and these steps.In some embodiments
In, being filtered through tangential flow filtration is carried out, such as cross-flow ultrafiltration.
In some embodiments, being filtered through perforated membrane is carried out.In some embodiments, perforated membrane is included in about 1-
Hole size in the range of 100kD.In some embodiments, hole size is in the range of about 1-50kD.In some embodiments,
Hole size is in the range of about 3-30kD.
In some embodiments, it is filtered through and sequentially passes through multiple perforated membranes to carry out.For example, in some embodiments
In, by solution of first membrane filtering comprising formed carbon quantum dot.Then the second membrane filtering filtrate is passed through.This
Afterwards, by the 3rd membrane filtering filtrate.In some embodiments, the perforated membrane for adopting in continuous filtration step has not
Same hole size.In some embodiments, the perforated membrane for adopting in continuous filtration step has the hole size for increasing successively.
For example, in some embodiments, first, second, and third perforated membrane has respectively the hole size of about 3kD, 10kD and 30kD.
Filtration can occur under numerous conditions.For example, in some embodiments, filter and occur to be depressed in about 0.1 air
Under the transmembrane pressure of about 10 atmospheric pressure.In some embodiments, filter occur about 0.5 air be depressed into about 2 atmospheric pressure across
Under film pressure.In some embodiments, filter and occur under about 1 atmospheric pressure.
The purifying of carbon quantum dot
In some embodiments, the step of disclosed method also includes purifying formed carbon quantum dot is (such as pure
Change the oxidant separated in solution).In some embodiments, purifying occurs in the required chi for selecting formed carbon quantum dot
Before, during or after very little step.In some embodiments, purification step including but not limited to extract, filter, evaporation,
Precipitation, dialysis and combinations thereof.
In some embodiments, purification step includes solution, filtering solution of the neutralization comprising formed carbon quantum dot
And dialysis solutions.In some embodiments, purification step includes solution of the dialysis comprising formed carbon quantum dot.One
In a little embodiments, purification step includes the formed carbon quantum dot of extraction from reactant mixture (such as solution).At some
In embodiment, extraction utilizes organic solvent, such as ethyl acetate or 2- butanol, or the combination of ethyl acetate and 2- butanol.Institute
Other purification process of the carbon quantum dot of formation are also predictable.
The raising of the quantum yield of carbon quantum dot
In some embodiments, disclosed method also includes the step of the quantum yield of the carbon quantum dot for improving formed
Suddenly.In some embodiments, there is the step of the required size of formed carbon quantum dot is selected it in the step that improves
Before, during or after.
The quantum yield of carbon quantum dot can be improved using various methods.Illustrative methods are included but is not limited to：At hydro-thermal
Reason carbon quantum dot；Carbon quantum dot is processed with one or more alkali (such as NaOH)；Use one or more hydroxide treatment
Carbon quantum dot；With one or more dopant (such as NaH2PO3) process carbon quantum dot；Carbon is processed with one or more reducing agent
Quantum dot；And combinations thereof.
In some embodiments, improve the quantum yield of carbon quantum dot is carried out by hydro-thermal process carbon quantum dot.
In some embodiments, hydro-thermal process is included in water uses hydroxide treatment carbon quantum dot, to increase its quantum yield.One
In a little embodiments, hydro-thermal process carbon quantum dot is included in container (such as seal pot), in the temperature higher than 100 DEG C (for example
About 180-200 DEG C of temperature) under, water process carbon quantum dot is used under stress.
In some embodiments, the quantum yield of carbon quantum dot is improved by processing carbon amounts with one or more reducing agent
Son is put to carry out.In some embodiments, reducing agent includes but is not limited to hydrazine, sodium borohydride, heat, light, sulphur, vulcanized sodium, sulphur
Sodium hydride and combinations thereof.
In some embodiments, the quantum yield of carbon quantum dot is improved at least about 50% by the step that improves, at least
About 100%, at least about 200%, or at least about 500%.In some embodiments, the step that improves is by carbon quantum dot
Quantum yield improves at least about 50%.In some embodiments, it is described to improve step by the quantum yield of carbon quantum dot from about
0.1% brings up to about 50%.
Advantage
By the required size for selecting carbon quantum dot, disclosed method can be used to the band of the carbon quantum dot for adjusting formed
Gap.Therefore, disclosed method can be used to produce the carbon quantum dot with required band gap.For example, in some embodiments, carbon
The band gap of quantum dot is in the range of about 0.5-5eV.In some embodiments, model of the band gap of carbon quantum dot in about 1-5eV
In enclosing.In some embodiments, the band gap of carbon quantum dot is in the range of about 1-5eV.In some embodiments, carbon quantum
The band gap of point is in the range of about 0.5-3eV.In some embodiments, the band gap of carbon quantum dot is in the range of about 1-3eV.
In some embodiments, the band gap of carbon quantum dot is in the range of about 2-3eV.In some embodiments, carbon quantum dot
Band gap is less than about 1.5eV.In some embodiments, the band gap of carbon quantum dot is less than about 3eV.
Therefore, disclosed method can be used to form the carbon quantum dot with required band gap in the way of it can amplify scale.
For example, in some embodiments, disclosed method can form large batch of carbon quantum dot.In some embodiments, institute
State high-volume in the range of about 1g carbon quantum dots to about 10 tons of carbon quantum dots.In some embodiments, the high-volume is
More than about 1g carbon quantum dots.In some embodiments, the high-volume is to exceed about 500g carbon quantum dots.In some embodiment party
In formula, the high-volume is to exceed about 1kg carbon quantum dots.
Other embodiment
With reference now to the other embodiment of the disclosure, provide the experimental result supported and for these embodiments.However,
Applicant is it is to be noted, that disclosure below is for illustration purposes only, and is not intended to limit by any way the theme being claimed
Scope.
Embodiment 1. is derived from the band gap processing of the graphene quantum dot of coal
In this embodiment, by with following two ways control graphene quantum dot (GQD) size come process by
The band gap of the luminescence generated by light GQD of anthracite synthesis：Chemical oxidation treatment and by cross-flow ultrafiltration separate；Or utilization rises successively
High temperature makes the step chemical synthesis of simplicity one that GQD attenuates.Synthesized with specific dimensions and band gap using these methods
GQD.According to size, functional group and defect, GQD launches the light from bluish-green (2.9eV) to orange red (2.05eV).These are found to be source
From the attribute of the GQD of coal provide deeper into see very clearly, and illustrate the life of the amplified scale of the GQD with required band gap
Product method.
In the first approach, by changing membrane pore size, GQD is separated by size using cross-flow ultrafiltration, so as to fast
Speed purifies them.This cross-flow ultrafiltration is used for the industrial technology of great scale, for industry and municipal water purifying, and is used for
Food separation.The launch wavelength of purified GQD depend on they size (according to quantum constraint effect) and they
Functional group and defect.
In second approach, applicant is not to adopt ultrafiltration, but is added by controlling the reaction temperature of oxidizing process
The band gap of work GQD, realizes thering is synthesizing by the GQD of the size of limit temperature, and its photoluminescent property covers visible spectrum.Temperature
Higher, GQD is less, and highlighting can control the convenience of local dimensional by oxidative cleavage.
In first reaction scheme, it is prepared for different size using oxidation chemistry reaction and cross-flow ultrafiltration technique
GQD.As shown in Figure 2 A, first thick anthracite is dispersed in the mixed solvent of sulfuric acid and nitric acid, then at a temperature of restriction
Heating 24 hours, obtains settled solution.After purifying, by tangential flow systems process under about 1 atmospheric pressure transmembrane pressure (TMP)
GQD solution, the system adopts successively hole size for 3kD, the film of 10kD and 30kD.
Fig. 2 C-F show transmission electron microscope (TEM) image and their correspondingly-sized of the GQD of initially-separate.Fig. 2 G and
Fig. 3 summarizes respectively the Hydrodynamic diameter and dynamic light scattering (DLS) analysis result obtained by TEM.
Size Distribution in Fig. 2 G is the statistical average of the sample size of about 150 particles in TEM image.Hydrodynamics is straight
The distribution in footpath is calculated by the light scattering in bulk solution.After purge process, TEM image shows that having obtained average-size is
4.5 ± 1.2,16 ± 3.3,41 ± 6.4 and 70 ± 15nm GQD.Corresponding Hydrodynamic diameter is respectively 10 ± 2.5,27 ±
7.9,41 ± 11 and 76 ± 18nm.The hydration layer that the size amplified in DLS analyses is attributed to around GQD.Corresponding GQD batches mark
GQDs-Sx is designated as, wherein " S " expression " detached ", " x " represents the average diameter from TEM image.
Using two kinds of solid state NMR experimental study materials using magic angle spin (MAS)：Directly13C pulses and1H-13C intersects
Polarization (CP).In the case, the latter be enough to characterize rich proton material.But, for the material that this paper is studied (may have
Larger shortcoming proton region), also using direct13C pulse means.
For all kinds of experiments, composed entirely (Fig. 4) using single group gain of parameter, it is therefore an objective at least obtain relevant each GQD sample
Qualitative information.Each experiment discloses obvious bands of a spectrum, and the maximum peak from aryl and thiazolinyl is at about 130ppm.
In most spectrograms, the signal (very likely from carbonyl) at about 170ppm is also apparent from.For each sample, aryl/thiazolinyl
Signal is with carbonyl signals direct13Relative intensity in C burst spectrums and CP spectrums is significantly different.Trial makes quantitative interpretation by needs
Various times of contact obtain CP spectrum and by multiple relaxation delays obtain it is direct13C burst spectrums.Anyway, from these
Full spectrum can be, it is evident that as GQD sizes increase, and carbonyl environment generates much broader change (such as from direct13C burst spectrums can
It is clearly visible), including ketone and carbonyl functional group.However, CP spectrums show, the cross polarization of the carbonyl in larger GQD is not as most
The cross polarization of the carbonyl in little GQD.
As GQD becomes big, the relative amount of carbonyl tails off.Equally, as GQD becomes big, shadow of the adjacent protons to peak intensity
Sound diminishes.These results are consistent with the graphite oxide structure of the GQD from coal.
The chemical constitution of GQD obtains x-ray photoelectron power spectrum (XPS) analysis with Fourier transform infrared (FTIR) analysis
It is further characterized by.The XPS of various sizes of GQD composes (Fig. 5 A) and shows entirely, and GQD is mainly made up of carbon and oxygen.As shown in Fig. 5 B-E,
The high-resolution C1s XPS of GQD shows that COOH and C-O peaks are respectively present in 288.8eV and 286.6eV.Fig. 5 F summarize these
The relative abundance of functional group.The description that proportional amount of quantitative assessment to aryl/thiazolinyl and carbonyl is tested not as NMR.In figure
In FTIR spectrums shown in 6A-D, in little GQD, C-H stretch modes occur in about 2980cm-1Place, and as GQD sizes increase,
This functional group becomes to be not easy to detect.Its reason is that, as GQD becomes big, edge C-H flexible abundance declines.Carbonyl is stretched
Contracting can be, it is evident that but between samples distribution relative intensity be more difficult.
The effect that GQD is separated by cross-flow ultrafiltration is further have rated by the photophysical property of the detached GQD of research institute
Power.Fig. 7 presents the UV- visible absorbances spectrum of GQD.Larger GQD tends in longer wavelength absorption, and less GQD
Absorb and blue shift occurs.The wide of larger GQD absorbs the complexity for being attributed to electronic state.
Fig. 8 A-E present the two-dimentional excitation-emission contour map of GQD.Under 365nm UV light, these quantum dot solutions
The light of transmitting is across the most of visible spectrum (Fig. 8 F) from green glow (about 2.4eV) to orange light (about 1.9eV) region.Fig. 8 G are total
The correlation between band gap and size or Molecular weight cut-off value is tied.As expected, when GQD sizes increase to 70nm from 4.5nm
When, peak emission occurs from about 520nm to the red shift of about 620nm, and this meets quantum constraint effect.Make reference mark with quinine sulfate
Standard, when GQD sizes increase to 70nm from 4.5nm, these GQD show 1.1%, 0.89%, 0.65% and 0.38% not
Same fluorescence quantum yield.
Quantum yield increases with size and reduces, and shows the defective effect that fluorescence is subject in GQD, because bigger GQD exists
There is less defective bit caused by oxidation in unit area, thus emissivity becomes less.The low quantum yield of these GQD
It is similar with published data.
As above reported, the simple hydro-thermal process in alkali improves quantum yield.For example, it is water-soluble in 0.2M NaOH
GQDs-S4.5 is heated in liquid, respectively quantum yield 8.1% and 10% (Fig. 9) is brought up in air and argon gas.When 100
At a temperature of DEG C, in 1M Na2When in the S aqueous solution GQD is processed 1 day, it was observed that similar raising.For example, Na2After S process,
About 5 times of the quantum yield increase (Fig. 9) of GQDs-S4.5.
Isolation technics can effectively produce the GQD with controlled size.For example, GQDs-S4.5, GQDs-S16, GQDs-S41
8%, 30%, 52% and 10% is respectively with the relative productivity of GQDs-S70.This represents 1.6% with anthracite as starting point,
6%, 10% and 2% yield based on weight.Therefore, the gross production rate of GQD is about 20%.
Second method for adjusting GQD sample sizes is by Direct synthesis technique rather than separation.A this step
The GQD of production size differentiation and be control based on to reaction temperature without the need for the short-cut method of cross-flow ultrafiltration.In different temperatures
The GQD that synthesis is obtained for 24 hours is labeled as GQDs-Tx-y, wherein " T " expression " temperature ", " x " indicates synthesis temperature, and " y " is indicated
The size obtained by TEM.Temperature is higher, and the degree of oxidation of generation is higher, and GQD is etched into into thinner size, causes to expand
Band gap.The change of GQD sizes is displayed in TEM image (Figure 11), wherein as synthesis temperature is increased to respectively 110 from 50 DEG C
DEG C, 130 DEG C and 150 DEG C, the average diameter of GQD is 54 ± 7.2,27 ± 3.8,25 ± 5.0 and 7.6 ± 1.8nm.Such as pass through
MALDI-MS is determined, and the corresponding molecular weight at GQD peaks is respectively 60,49,44 and 27kD (Figure 12).
As expected, under the diameter that 100 DEG C of GQD for preparing simultaneously Jing cross-flow ultrafiltrations are measured by TEM with different temperatures
The GQD scopes of synthesis are coincide good.When Fig. 2 G and 11E are made into composite diagram (Figure 13), this point becomes more apparent upon.On GQD
Functional group's ratio also changes with synthesis temperature.
It is detached with by cross-flow ultrafiltration13C MAS NMR GQD are similar to, and these GQD synthesized under different temperatures are main
Show and there is carbonyl and aryl/thiazolinyl in about 170ppm and 130ppm respectively.Synthesis temperature is increased to into 150 DEG C of generations more equal
Even structure, because aryl/thiazolinyl and carbonyl signals are significantly sharpened.Directly13The difference pair that C burst spectrums are composed with cross polarization
It is particularly pertinent for GQDs-T110-27.Direct13In C pulse tests, aliphatic carbons are substantially with very length13C spins-brilliant
The lattice relaxation time, therefore provide very weak signal.1H-13In C cross polarizations experiment,1H spin-lattice relaxation times are so short that
It is many so that these aliphatic impurity can be from various-O-C (sp3) and-O-C (sp3)-O-ring is more easily detected by border.
As shown in Figure 10 A-E, high-resolution C1s XPS spectrum shows, as synthesis temperature is increased to 150 DEG C from 50 DEG C,
The percentage of COOH functional groups increases to about 22% from about 4%, while C-C linkage contents are reduced to about 65% from about 93%.From calmly
Property angle see that correspondence change in H NMR spectroscopy (170ppm higher nearby signal and the aryl/thiazolinyl intensity for reducing) is tied with XPS
Fruit is consistent.However, non-carboxyl C-O contents keep constant in whole temperature range.
Applicant further study the UV- visible absorptions of the GQD synthesized under different temperatures and two-dimentional excitation-emission.
The absorption spectra (Figure 15) of the GQD synthesized under different temperatures is similar to the absorption spectra of the GQD prepared by cross-flow ultrafiltration.Higher
Synthesis temperature under, absorption curve slope is in low wavelength region.Under low synthesis temperature, absorption is tended in whole visual field
It is wider.
Applicant further study the control by reaction temperature to GQD band gap by the emission characteristic of analysis GQD.Such as
Shown in Figure 16 A-E, when temperature from be increased to 150 DEG C for 50 DEG C when, emission peak is displaced to about 420nm from about 580nm, be distributed corresponding to
Orange red and bluish-green transmitting light color.As temperature drops to 50 DEG C from 150 DEG C, maximum excitation is also displaced to about from about 320nm
300nm.This red shift of maximum excitation is attributed to band gap and narrows under relatively low synthesis temperature.Can be intuitive to see in Figure 16 F
The change of band gap, wherein GQD solution are launched from blue-green to orange-red light in the case where 365nm excites UV lamp.Figure 16 G summarize temperature
Spend the impact to the processing of GQD band gap.When excitation wavelength from 300nm change to 320nm when, emission maximum is without significant change.From
130 DEG C to the 150 DEG C suddenly increases for observing band gap.
As Figure 10 E collect, at higher temperatures, COOH contents increase and C-C contents decline.It is not only restricted to theory,
It is contemplated that, the gap tunable of GQD can simultaneously be attributed to dimensional effect and functional group's effect.
Because the graphite-structure in bituminous coal is less, the GQD for being directly synthesized transmitting blue light by bituminous coal can be easier.Such as Figure 17
It is shown, launch blue light under 365nm UV lamps in 120 DEG C of GQD extracted from bituminous coal.
By research in the property of 130 DEG C of GQD synthesized with the differential responses time, the reaction time is also evaluated to adjusting
The impact of GQD band gap.As shown in figure 18, react 1 hour and the peak emission of the reaction GQD of 6 hours does not show substantially partially
Move, show that the reaction time has not significant impact to emission maximum.Conversely, temperature is only the decisive factor for adjusting GQD band gap.Not only
Thus, from coal GQD band gap it is convenient control the reason for be in coal two-dimentional crystal domain size compared with the crystal domain size in graphite
Inherently less (Figure 19), further consists in the defect of product.
Sum it up, applicant has developed two kinds of approach are obtaining the GQD with controlled band gap.One kind is using tangential
Stream ultrafiltration separates GQD by size, and another kind is direct controlling reaction temperature, the final GQD sizes of the reaction temperatures affect.Root
According to size and functional group, these GQD show the Photoluminescence from green glow to orange light.Adjustable transmission and fluorescence quantum yield
Show, launch from eigenstate transmitting and defect state from the luminescence generated by light of the GQD of coal.
The material of embodiment 1.1
Anthracite [Fei Sheer scientific companies (Fisher Scientific), catalog number：S98806], bituminous coal (take house
That scientific company, catalog number：S98809), graphite [Sigma-aldrich corp (Sigma-Aldrich), product
Catalog number (Cat.No.)：332461, B150mm pieces], H2SO4(95-98%, Sigma-aldrich corp) and HNO3(70%, western lattice
Agate-aldrich corp) used with the state of buying, unless otherwise noted.Using polytetrafluoroethylene film [Sai Duolisi companies
(Sartorius), lot number 11806-47-N] and dialysis bag [membrane filtration product limited company
(MembraneFiltration Products, Inc.), production number：1-0150-45] purifying GQD.Cross-flow ultrafiltration instrument is
The Krosflo Research II i TFF systems of Shi Bichun companies (Spectrum Labs).Milipore filter is by modified poly (ether-sulfone)
Obtained hollow membrane.Milipore filter also is available from Shi Bichun companies (production number：D02-Exxx-05-S).
Embodiment 1.2 prepares the GQD for cross-flow ultrafiltration
In typical program, 6g anthracites are scattered in the mixed solvent of 225mL sulfuric acid and 75mL nitric acid.With ultrasound
Instrument [Cole Pa Mo companies (Cole Parmer), model 08849-00] processes solution 2 hours, then heats 1 day at 100 DEG C.
After thermal oxide, the brown-red solution clarified is obtained.Then solution is cooled down in ice-water bath, with deionization (DI) water three is diluted
It is secondary.Then, solution in 1000 dalton dialysis bags relative to DI water dialysis 3 days.
Embodiment 1.3 separates GQD by cross-flow ultrafiltration
As shown in Figure 2 B, the GQD of initial preparation is separated using cross-flow ultrafiltration.Logical via size is respectively 3 kilodaltons
(kD), 10kD different with the three of 30kD kinds films carries out successively ultrafiltration.The transmembrane pressure (TMP) of film is about 1 atmospheric pressure.
In whole experiment, about 50-100mL/min is maintained to constant flow rate.
As hole size and TMP increase, the permeability of GQD increases.Therefore, by using suitable film size and TMP value,
Obtain the GQD of different size distribution.When diffusate becomes colorless from brown, film is changed.It is little that each separation batch carries out 1-2
When.
Embodiment 1.4 prepares at different temperatures GQD
In typical program, 3g anthracites are scattered in the mixed solvent of 225mL sulfuric acid and 75mL nitric acid.With ultrasound
Instrument [Cole Pa Mo companies (Cole Parmer), model 08849-00] processes solution 2 hours, then in different temperatures (50-
150 DEG C) under heat 1 day.After thermal oxide, the brown-red solution clarified is obtained.Then solution is cooled down in ice-water bath, spend from
Sub- water (DI water) dilutes three times.Then, solution in 1000 dalton dialysis bags relative to DI water dialysis 3 days.
Embodiment 1.5 improves quantum yield by NaOH process
In typical program, the 15mL solution comprising 1mg/mL GQD in the 0.2M NaOH aqueous solution is prepared, by its turn
The teflon autoclave of sealing is moved to, 180 DEG C is heated to and is kept for 1 day.After being cooled to room temperature, the solution is transferred to into 1000 roads
That dialysis bag, relative to DI water dialysis 3 days.
Embodiment 1.6 passes through Na2S process improves quantum yield
In typical program, prepare in round-bottomed flask in 1M Na215mL solution comprising 1mg/mL GQD in S.
The solution is heated to into 100 DEG C under nitrogen atmosphere, is kept for 1 day.After being cooled to room temperature, the solution is transferred to into 1000 dalton and is oozed
Analysis bag, relative to DI water dialysis 3 days.
The sample characterization of embodiment 1.7
Using 2100F Flied emission rifle TEM, GQD is transferred directly to into C-flatTMOn transmission electron microscope (TEM) grid, shoot
TEM image.In the enterprising Mobile state light scattering experiments of the Zetasizer of Zen 3600 of Malvern company (Malvern), refractive index
For 2, temperature is 25 DEG C.X-ray photoelectron power spectrum (XPS) is determined on PHI Quantera SXM scanning X-ray microprobes,
The angle of emergence is 45 °, and electron beam dimensions are 100 μm.For high resolution scanning, it can be 140eV and 26eV that full spectrum is logical.Scan it
Before, sputter [the Desk V sputter systems of Dan Dun companies (Denton)] the 2nm Au layers on sample surfaces.Raman microscopic spectrum is used
The Raman microscope of Reinshaw company (Renishaw) is obtained at room temperature, using 514nm laser excitations.Mass spectrum is public in Brooker
Obtain on the Autoflex MALDI ToF instruments of department (Bruker).Ultraviolet-visible (UV) spectrum is in Shimadzu Corporation
(Shimadzu) record on UV-2450 ultraviolet-visible spectrometers.In the JovinYvon of Huo Liba companies (HORIBA)
Stable state spectrum is obtained in Fluorolog 3.Solid-state FTIR spectrum is furnished with MCT/B survey meters Buddhist nun's high-tensile strength company (Nicolet)
FTIR microscopes on obtain.13C nuclear magnetic resonance (NMR) tests the Avance III 4.7T spectrometers in Brooker company
(50.3MHz 13C,200.1MHz 1H carry out on), standard broadband MAS probes of the spectrometer with the design of promising 4mm motors.Directly13C burst spectrums are obtained under the following conditions：12kHz MAS, 90 ° of pulses, 20.5ms FID, 10s relaxation delays, different scanning
Number (GQDs-S4.51440 time；GQDs-S16 1600 times, GQDs-S41 3400 times, GQDs-S70 3280 times, GQDs-T150-
7.6 9024 times, GQDs-T130-25 16928 times, GQDs-T110-27 8096 times, GQDs-T50-54 6328 times), each
FID is through the broadening process of 50Hz (1ppm) line.Directly13C burst spectrums are obtained under the following conditions：7.6kHz MAS, 90 ° of pulses,
20.5ms FID, 5s relaxation delay, different scanning number of times (GQDs-S4.5 10600 times；GQDs-S16 1600 times, GQDs-
S413400 time, GQDs-S70 10400 times, GQDs-T150-7.6 30632 times, GQDs-T130-25 16928 times, GQDs-
T110-27 8096 times, GQDs-T50-54 6328 times), each FID is through the broadening process of 50Hz (1ppm) line.To GQDs-
T150-7.6 and GQDs-T130-25 has carried out more scannings, to compensate the limited quantity of derived sample.
The transmembrane pressure equation of embodiment 1.8
Equation for calculating transmembrane pressure is as follows：
In above equation, PF,PRAnd PPIt is respectively the pressure of charging, retention and penetrant.Used in cross-flow ultrafiltration
TMP value be constantly maintained at about 1 atmospheric pressure.
The quantum yield of embodiment 1.9 is calculated
Equation for calculating quantum yield is as follows：
In above equation, ΦiAnd ΦrIt is respectively the quantum yield of sample and reference substance.The integration of sample and reference substance is strong
Degree (area) is respectively IiAnd Ir。AiAnd ArIt is respectively absorptivity, niAnd nrIt is respectively the refractive index of sample and reference substance solution.
The calculating of embodiment 1.10XRD interplanar distance
Equation for calculating interplanar distance is as follows：
2dsin (θ)=n λ
In above equation, d is interplanar distance, and θ is XRD peaks, and λ is X-ray wavelength (copper source, λ=0.154059nm).This
Equation can be used to the interplanar distance of (002) crystal structure for calculating anthracite and graphite.
The calculating of the Hydrodynamic diameter of embodiment 1.11
The Hydrodynamic diameter shown in Fig. 3 is calculated using below equation：
Embodiment 2. prepares the alternative of graphene quantum dot
This example provides can be with the additive method of synthesizing graphite alkene quantum dot.This includes only using nitric acid.It is also wrapped
Include after completion of the reaction using by evaporating the step of removing nitric acid.It is also included with ethyl acetate or ethyl acetate/2- butanol
Mixture extracts GQD from acid solution, then evaporation of organic solvent.
Embodiment 2.1 synthesizes the process of GQD in mixed acid from anthracite
2.5g anthracites are suspended in the concentrated sulfuric acid (60mL) and nitric acid (40mL).Then 100 DEG C will reaction stirring and
Heating 15 hours.Solution is cooled to into room temperature, the beaker equipped with 200mL cold water is poured slowly into.Then sintered filter mistake is passed through
Filter reactant mixture, removes black solid.Next, with 150mL 2- butanol/ethyl acetate, (60/40) v/v extracts 150mL
Filtrate.Organic layer MgSO4It is dried, and is filtered by sintered filter.Using rotary evaporation concentrate solution, solid GQD is obtained.
Finally, GQD solids are dried 15 hours in 60 DEG C of vacuum drying ovens.GQD solids (21% yield) are partially soluble in water.Can be as front
Size Selection is carried out by tangential flow filtration described in text.
Embodiment 2.2 synthesizes the process of GQD in nitric acid from anthracite
5g anthracites are added into the round-bottomed flask equipped with splash bar, with 90mL 70%HNO3Mixing.While stirring will be scattered
Coal is heated to backflow, continues 17 hours, is subsequently cooled to room temperature.By sintered filter filtering solution, then steamed using rotation
Send out and remove HNO3.Dry rufous graphene quantum dot powder is obtained, yield is 44%.Slipstream can as mentioned before be passed through
Filtration carries out size Selection.
Embodiment 2.3 synthesizes the process of GQD in nitric acid from bituminous coal
Red fuming nitric acid (RFNA) (100mL) is added into bituminous coal (4.0g).Then under reflux by suspension heating 18 hours.It is cooled to room
Wen Hou, deionized water is extracted with ethyl acetate 3mL etc. point of suspension dilution twice (5 parts, every part of 4mL).Organic layer sulphur
Sour sodium is dried, and reduced pressure concentration.Then concentrate is added into hexane, is settled out orange solids, the further vacuum of the orange solids
It is dried 24 hours, obtains 50mg products (or 38% extrapolation yield).Or, concentrate can be by vacuum (0.1mm Hg)
In be heated to 60 DEG C and carry out drying, produce 42% solid product.As mentioned before size Selection can be carried out by tangential flow filtration.
Need not further repeat, applicant believes that, by means of the explanation of this paper, those skilled in the art can be at utmost
Using present disclosure.Embodiment as herein described is interpreted as illustrative, rather than limits the disclosure by any way
The remainder of content.Although various embodiments have been illustrated and described, those skilled in the art are without departing substantially from this
In the case of bright spirit or teaching, can to its many changes may be made and improve.Therefore, protection domain be not only restricted to above to
The description for going out, and should only be limited by the claims included below, including all equivalents of claimed subject matter.Cited herein
By reference to being incorporated into herein, its scope is to provide and this paper institutes the disclosure of all patents, patent application and publication
State consistent and and make supplementary procedural details or other details to described herein.
Claims (55)
1. there is the production method of the amplified scale of the carbon quantum dot of required band gap, methods described includes：
Carbon source catalytic oxidation agent at the reaction temperatures is made, wherein described contact the formation for causing carbon quantum dot；And
Select required size the carbon quantum dot for being formed, wherein it is described selection include it is following at least one：
The carbon quantum dot for being formed with required size is separated with the carbon quantum dot that other are formed；
Reaction temperature is selected, to produce the carbon quantum dot for being formed of required size；And
Combinations thereof.
2. the method for claim 1, wherein the contact include in the presence of an oxidizer carrying out carbon source it is ultrasonically treated.
3. the method for claim 1, wherein the contact is included at the reaction temperatures, in the presence of an oxidizer to carbon source
Heated.
4. method as claimed in claim 3, wherein the reaction temperature is at least about 100 DEG C.
5. method as claimed in claim 3, wherein the reaction temperature is in the range of about 100-150 DEG C.
6. the method for claim 1, wherein the carbon source is selected from the group：Coal, coke, graphite, CNT, activity
Charcoal, carbon black, fullerene and combinations thereof.
7. the method for claim 1, wherein the carbon source includes coal.
8. method as claimed in claim 7, wherein the coal is selected from the group：Anthracite, bituminous coal, ub-bituminous coal, grade metamorphic bituminous, drip
Blue or green alkene, pitch, mud coal, brown coal, thermal coal, petrochemical industry oil and combinations thereof.
9. the method for claim 1, wherein the carbon source includes anthracite.
10. the method for claim 1, wherein the carbon source includes bituminous coal.
11. the method for claim 1, wherein the oxidant includes acid.
12. methods as claimed in claim 11, wherein the acid is selected from the group：Sulfuric acid, nitric acid, phosphoric acid, hypophosphorous acid, oleum
Acid, hydrochloric acid, pyrosulfuric acid, chlorosulfonic acid and combinations thereof.
13. the method for claim 1, wherein the oxidant is the mixture of sulfuric acid and nitric acid.
14. the method for claim 1, wherein the oxidant includes nitric acid.
15. the method for claim 1, methods described also includes the step of purifying formed carbon quantum dot.
16. methods as claimed in claim 15, wherein the purifying occurs in the carbon quantum for being formed for selecting required size
Before the step of point.
17. methods as claimed in claim 15, wherein the purifying is selected from the group：Extraction, filter, evaporation, precipitation, dialysis and
Its combination.
18. methods as claimed in claim 15, wherein the purifying includes extracting formed carbon amounts from reactant mixture
Sub- point.
19. methods as claimed in claim 15, wherein the purifying includes：
Solution of the neutralization comprising formed carbon quantum dot；
Filter the solution；And
Solution described in dialysis.
20. the method for claim 1, methods described also includes the step of improving the quantum yield of carbon quantum dot.
21. methods as claimed in claim 20, wherein described improve by hydro-thermal process carbon quantum dot, use one or more alkali
Process carbon quantum dot, carbon quantum dot is processed with one or more hydroxide treatment carbon quantum dot, with one or more dopant,
Process carbon quantum dot and combinations thereof to carry out with one or more reducing agent.
22. methods as claimed in claim 20, wherein the raising is carried out by hydro-thermal process carbon quantum dot.
23. methods as claimed in claim 20, wherein described improve by processing carbon quantum dot with one or more reducing agent
Come carry out.
24. methods as claimed in claim 23, wherein the reducing agent is selected from the group：Hydrazine, sodium borohydride, heat, light, sulphur, sulphur
Change sodium, NaHS and combinations thereof.
25. the method for claim 1, wherein the selection includes selecting reaction temperature, to produce the institute of required size
The carbon quantum dot of formation.
26. methods as claimed in claim 25, wherein, selected reaction temperature is to keep constant during contact procedure to set
Constant temperature degree.
27. methods as claimed in claim 25, wherein selected reaction temperature is in the range of about 25-200 DEG C.
28. methods as claimed in claim 25, wherein selected reaction temperature is in the range of about 50-150 DEG C.
29. methods as claimed in claim 25, wherein selected reaction temperature is in the range of about 100-150 DEG C.
30. methods as claimed in claim 25, the wherein required size of carbon quantum dot subtract as selected reaction temperature increases
It is little.
31. the method for claim 1, wherein the selection is included the carbon quantum dot for being formed with required size
Separate with the carbon quantum dot that other are formed.
32. methods as claimed in claim 31, wherein the separation includes filtering.
33. methods as claimed in claim 32, wherein the filtration is selected from the group：Coarse filtration, micro-filtration, ultrafiltration, tangential flow filtration,
Cross-flow ultrafiltration, membrane filtration, dialysis and combinations thereof.
34. methods as claimed in claim 32, wherein the perforated membrane that is filtered through is carried out.
35. methods as claimed in claim 34, wherein the perforated membrane is included in the hole size in the range of about 1-100kD.
36. methods as claimed in claim 32, wherein described being filtered through sequentially passes through multiple perforated membranes to carry out.
37. methods as claimed in claim 36, wherein the perforated membrane has different hole sizes.
The required size of 38. the method for claim 1, wherein carbon quantum dot includes size range.
39. the method for claim 1, wherein the scope of the required size of the carbon quantum dot is about 1nm diameters to about
200nm diameters.
40. the method for claim 1, wherein the scope of the required size of the carbon quantum dot is about 1nm diameters to about
100nm diameters.
41. the method for claim 1, wherein the scope of the required size of the carbon quantum dot is about 2nm diameters to about
80nm diameters.
42. the method for claim 1, wherein carbon quantum dot include graphene quantum dot.
43. the method for claim 1, wherein carbon quantum dot are functionalized with multiple functional groups.
44. methods as claimed in claim 43, wherein the functional group is selected from the group：Amorphous carbon, epoxide, carbonyl, carboxyl,
Aryl, alkyl, thiazolinyl, ketone group, ester, amine, acid amides and combinations thereof.
45. the method for claim 1, wherein carbon quantum dot carry out edge functionalization with multiple functional groups.
46. the method for claim 1, wherein carbon quantum dot have individual layer.
47. the method for claim 1, wherein carbon quantum dot have multiple layers.
48. methods as claimed in claim 47, wherein carbon quantum dot have about two-layer to about four layers.
49. the method for claim 1, wherein carbon quantum dot have crystallization hexagonal structure.
50. the method for claim 1, wherein carbon quantum dot are luminescence generated by lights.
51. the method for claim 1, wherein carbon quantum dot have the band gap in the range of about 0.5-3eV.
52. the method for claim 1, wherein carbon quantum dot have the band gap in the range of about 2-3eV.
53. the method for claim 1, wherein methods described form carbon quantum dot with high-volume.
54. methods as claimed in claim 53, wherein described high-volume is to exceed about 1kg carbon quantum dots.
55. methods as claimed in claim 53, wherein the high-volume is in about 1g carbon quantum dots to about 10 tons of carbon quantum dots
In the range of.
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| PCT/US2015/036729 WO2016053411A1 (en) | 2014-06-19 | 2015-06-19 | Bandgap engineering of carbon quantum dots |
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| JP (1) | JP2017525645A (en) |
| KR (1) | KR20170023079A (en) |
| CN (1) | CN106573778A (en) |
| AU (1) | AU2015324578A1 (en) |
| CA (1) | CA2952960A1 (en) |
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| RU (1) | RU2017101486A (en) |
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| CN107381536A (en) * | 2017-06-08 | 2017-11-24 | 四川大学 | A kind of quick, method for being prepared on a large scale water-solubility fluorescent carbon quantum dot |
| CN107804841A (en) * | 2017-12-14 | 2018-03-16 | 北方民族大学 | Hydro-thermal acid vapor fullerene opens the method that cage method high yield prepares graphene quantum dot |
| CN107804840A (en) * | 2017-12-14 | 2018-03-16 | 北方民族大学 | The method that hydro-thermal cutting high yield prepares coal base graphene quantum dot |
| CN109019560A (en) * | 2018-10-16 | 2018-12-18 | 吕梁学院 | A kind of preparation method of coal-based carbon point |
| CN109205598A (en) * | 2018-11-16 | 2019-01-15 | 重庆大学 | The purposes of graphene-based compound, graphene-based compound and preparation method thereof |
| CN109266338A (en) * | 2018-10-26 | 2019-01-25 | 陕西科技大学 | A kind of fowler alkenyl carbon quantum dot and preparation method thereof |
| CN109354014A (en) * | 2018-11-30 | 2019-02-19 | 中南大学 | A kind of graphitized carbon quantum dot and preparation method thereof |
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| JP2016525997A (en) | 2013-05-02 | 2016-09-01 | ウィリアム・マーシュ・ライス・ユニバーシティ | Method for generating graphene quantum dots from coal and coke |
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| CN107804841A (en) * | 2017-12-14 | 2018-03-16 | 北方民族大学 | Hydro-thermal acid vapor fullerene opens the method that cage method high yield prepares graphene quantum dot |
| CN107804840A (en) * | 2017-12-14 | 2018-03-16 | 北方民族大学 | The method that hydro-thermal cutting high yield prepares coal base graphene quantum dot |
| CN107804840B (en) * | 2017-12-14 | 2019-10-15 | 北方民族大学 | The method that hydro-thermal cutting high yield prepares coal base graphene quantum dot |
| CN109019560A (en) * | 2018-10-16 | 2018-12-18 | 吕梁学院 | A kind of preparation method of coal-based carbon point |
| CN109266338A (en) * | 2018-10-26 | 2019-01-25 | 陕西科技大学 | A kind of fowler alkenyl carbon quantum dot and preparation method thereof |
| CN109205598A (en) * | 2018-11-16 | 2019-01-15 | 重庆大学 | The purposes of graphene-based compound, graphene-based compound and preparation method thereof |
| CN109354014A (en) * | 2018-11-30 | 2019-02-19 | 中南大学 | A kind of graphitized carbon quantum dot and preparation method thereof |
| CN109354014B (en) * | 2018-11-30 | 2020-07-31 | 中南大学 | Graphitized carbon quantum dot and preparation method thereof |
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| JP2017525645A (en) | 2017-09-07 |
| IL249614A0 (en) | 2017-02-28 |
| SG11201610613XA (en) | 2017-01-27 |
| AU2015324578A1 (en) | 2017-02-02 |
| WO2016053411A1 (en) | 2016-04-07 |
| CA2952960A1 (en) | 2016-04-07 |
| KR20170023079A (en) | 2017-03-02 |
| EP3157868A4 (en) | 2017-11-29 |
| RU2017101486A (en) | 2018-07-20 |
| EP3157868A1 (en) | 2017-04-26 |
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