CN105460922B - Partial reduction graphene oxide FRET nano-probe and preparation method thereof - Google Patents

Partial reduction graphene oxide FRET nano-probe and preparation method thereof Download PDF

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CN105460922B
CN105460922B CN201510852835.4A CN201510852835A CN105460922B CN 105460922 B CN105460922 B CN 105460922B CN 201510852835 A CN201510852835 A CN 201510852835A CN 105460922 B CN105460922 B CN 105460922B
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graphene oxide
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CN105460922A (en
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陈伟
王艳红
唐淑榕
邓豪华
李光文
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Fujian Medical University
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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Abstract

The present invention discloses a kind of partial reduction graphene oxide FRET nano-probe and preparation method thereof, and it is to prepare partial reduction graphene oxide by room temperature control reduction of the graphene oxide in alkaline solution.Preparation method of the present invention has environmental protection, simple and efficient to handle, high repeatability and other advantages.The stannic oxide/graphene nano probe of prepared partial reduction has larger sp2Hydridization region, less surface defect and good dispersiveness and stability.The fluorescent quenching efficiency and quenching speed that prepared partial reduction graphene oxide modifies fluorescence molecule single stranded DNA are increased substantially, and are a kind of ideal FRET nano-probes.

Description

Partial reduction graphene oxide FRET nano-probe and its preparation Method
Technical field
The present invention relates to partial reduction graphene oxide FRET nano-probe and preparation method thereof, belong to Field of nanometer technology.
Background technology
Graphene（graphene）It is the tightly packed hydridization single layer of carbon atom crystal into bi-dimensional cellular shape lattice structure, it is thick It is but also most hard nano material that degree only 0.335 nm, which is that world is most thin at present,.Graphite through peroxidating peel off obtained by it is derivative Thing-graphene oxide（graphene oxide, GO）, there are the oxy radicals such as substantial amounts of hydroxyl, carboxyl, carbonyl on its surface, these The presence of functional group causes graphene oxide to have fabulous hydrophily, stable micella can be formed in water solution system molten Liquid, while having good chemical modifiability, is often used as the carrier of recognition component in bio-sensing research.
FRET is that energy is transferred to acceptor fluorescence group by donor fluorophore through radiationless approach, and is caused Donor fluorescent is quenched optical phenomena enhanced with acceptor fluorescence.In recent years, people are directed to exploitation based on graphene oxide fluorescence The FRET sensor of quenching effect, and use it for biological and chemical detection.Research shows, graphene oxide With single stranded DNA（ssDNA）With stronger suction-operated to double-stranded DNA（dsDNA）Adsorption capacity it is weaker.Fluorescence molecule is repaiied The ssDNA of decorations can be adsorbed on surface of graphene oxide, cause fluorescent quenching by FRET.If fluorescence molecule is repaiied The ssDNA of decorations be complementary to chain hybridize to be formed after double-strand can not then be oxidized graphene absorption, so as to keep fluorescent characteristic.With it Its organic quencher is compared, and graphene oxide does not only have higher quenching efficiency, signal to noise ratio, and it is peculiar to possess nano material institute Advantage, can protect the biomolecule stability of its surface modification, digestion be prevented, in DNA, RNA, protein, heavy metal ion And the context of detection of small-molecule substance has broad application prospects.
The invention provides a kind of partial reduction graphene oxide FRET nano-probe and its preparation New method.Partial reduction graphene oxide controls reduction to obtain by room temperature of the graphene oxide in alkaline solution, is keeping On the basis of water solution system stability, sp is effectively increased2Hydridization domain, modifies fluorescence molecule ssDNA fluorescent quenching Efficiency and quenching speed are increased substantially, and are a kind of preferable FRET nano-probes.
The content of the invention
It is an object of the invention to provide a kind of partial reduction graphene oxide FRET nano-probe and system Preparation Method.
To achieve these goals, the present invention uses following technical scheme：A kind of partial reduction graphene oxide fluorescence is total to Energy transfer of shaking nano-probe, it is characterized in that lamellar spacing be 1.1 nm, 2 (001) be 10.86 ° ~ 11.10 °, 2 (002) it is 22.10 ° ~ 22.66 °, C/O ratios are 0.49 ~ 0.53, and carbon-carbon bond ratio is 34.22% ~ 52.46%, can be quenched fluorescence The fluorescence of molecular modification single stranded DNA.
The Fluorescence quenching effect strengthens with the increase of carbon-carbon bond ratio.
In the partial reduction graphene oxide FRET nano-probe that 15 μ L concentration are 100 μ g/mL, plus Enter the 6- Fluoresceincarboxylic acids modification ssDNA and mmol/L, the pH 8.0 of 445 μ L 10 that 40 μ L concentration are 500 nmol/L contains 50 Mmol/L NaCl and 1 mmol/L EDTA Tris-HCl buffer solutions, react at room temperature 30 seconds, fluorescent quenching rate be 44.5 ~ 99.3%。
A kind of preparation method of partial reduction graphene oxide FRET nano-probe of the present invention, It is characterized in that graphene oxide water solution is mixed in equal volume with the NaOH aqueous solution, after room temperature reaction, centrifugation washing precipitates constant temperature Dry, obtain partial reduction graphene oxide solid, by partial reduction graphene oxide solid add water ultrasound peel off what must be stablized Partial reduction graphene oxide water solution.
It is above-mentioned used in graphene oxide preparation method be：The mixing that crystalline flake graphite is added into the concentrated sulfuric acid and phosphoric acid is molten In liquid, after being sufficiently stirred for, it is placed in 0 DEG C of ice bath, potassium permanganate is multiple on a small quantity, it is slowly added into solution mixed above, Keep after 0 DEG C of ice bath, magnetic agitation, the blackish green suspension of gained is transferred in tepidarium and obtains blackish green suspension, then by institute Obtain blackish green suspension to be transferred in tepidarium, reaction obtains atropurpureus suspension, and frozen water is slowly added into obtained atropurpureus In suspension, acquisition solution is stirred vigorously, then toward hydrogenperoxide steam generator is added dropwise dropwise in solution, solution colour sports bright orange The G1 sand core funnels filtering of 20-30 microns of resulting solution via hole diameter, is then centrifuged, abandoning supernatant after color, stirring；Precipitation Distilled water is added in thing and fully vibrates washing, is centrifuged, abandoning supernatant, precipitation color is in khaki；Hydrochloric acid is added to fill Divide vibration washing, the G1 sand core funnels filtering of 20-30 microns of via hole diameter removes insoluble particles, filtrate centrifugation, supernatant discarding Liquid, precipitation color continues to deepen；Then it is neutral sediment to be washed till into pH value with absolute ethyl alcohol, is centrifuged, abandoning supernatant, Precipitation is in brown color；Finally precipitated with washed with ether, the G5 sand core funnels filtering of 1.5-2.5 microns of via hole diameter, filter cake is in room temperature It is lower to dry overnight, obtain the graphene oxide of brown.
The concentration of the NaOH aqueous solution is the mmol/L of 20 mmol/L ~ 10.
The reaction time is 0.5 ~ 2 hour.
The freeze-day with constant temperature temperature is 50 ~ 60 DEG C, and drying time is 6 ~ 12 hours.
It is above-mentioned used in graphene oxide preparation method be：The g of 325 mesh crystalline flake graphite 2.7 is weighed, 316 mL are added to In the mixed solution of phosphoric acid that the concentrated sulfuric acid and 36 mL concentration that concentration is 18.4 mol/L are 14.7 mol/L, after being sufficiently stirred for, It is placed in 0 DEG C of ice bath, 16.2 g potassium permanganate are multiple on a small quantity, it is slowly added into solution mixed above, keeps 0 DEG C of ice The blackish green suspension of gained is transferred in 35 DEG C of tepidariums by bath, magnetic agitation after 3 hours, temperature control 1 hour, then by gained ink Green suspension is transferred in 50 DEG C of tepidariums, and temperature control 12 hours, 360 mL frozen water are slowly added into obtained atropurpureus suspension In mixture, 1 hour is stirred vigorously, then toward 12 mL 30wt% hydrogenperoxide steam generators, solution colour are added dropwise dropwise in solution Glassy yellow is sported, is stirred 30 minutes, the G1 sand core funnels filtering of 20-30 microns of resulting solution via hole diameter, then 4000 turns Centrifugation per minute 30 minutes, abandoning supernatant；Add 180 mL distilled waters and fully vibrate washing, 4000 rpms of centrifugations 30 Minute, abandoning supernatant, precipitation color is in khaki；Add 180 mL 30wt% hydrochloric acid and fully vibrate washing, via hole diameter 20- 30 microns of G1 sand core funnels filtering removes insoluble particles, and 4000 rpms of filtrate is centrifuged 30 minutes, and abandoning supernatant is sunk Shallow lake color continues to deepen；Then it is neutral sediment repeatedly to be washed till into pH value with absolute ethyl alcohol, and 4000 rpms centrifuge 30 points Clock, abandoning supernatant, precipitation is in brown color；Finally precipitated with washed with ether, the G5 sand core funnel mistakes of 1.5-2.5 microns of via hole diameter Filter, filter cake dries overnight at room temperature, obtains the graphene oxide of brown.
The present invention concrete technical scheme be：
（One）The preparation of graphene oxide
325 mesh crystalline flake graphites are weighed, it is 9 to be added to volume ratio:In 1 concentrated sulfuric acid and phosphoric acid mixed solution.It is sufficiently stirred for Afterwards, it is placed in 0 DEG C of ice bath.Potassium permanganate is multiple on a small quantity, it is slowly added into solution mixed above.0 DEG C of ice bath is kept, After magnetic agitation 3 hours, the blackish green suspension of gained is transferred in 35 DEG C of tepidariums, temperature control 1 hour, then again by suspension It is transferred in 50 DEG C of tepidariums, temperature control 12 hours.A certain amount of mixture of ice and water is slowly added into obtained atropurpureus to be suspended In liquid, it is stirred vigorously 1 hour.Then toward 30% hydrogenperoxide steam generator is added dropwise dropwise in solution, sported to solution colour bright orange Color.Resulting solution is through G1 sand core funnels（Aperture 20-30 microns）Filtering, then 4000 revs/min centrifuge 30 minutes, respectively through Washing once, once, alcohol is washed till neutrality for pickling, finally with after washed with ether through G5 sand core funnels（Aperture 1.5-2.5 microns）Cross Filter.Filter cake dries overnight at room temperature, obtains graphite oxide.
（Two）The preparation of partial reduction graphene oxide FRET nano-probe
By the 4 mg/mL above methods prepare graphene oxide water solution respectively with 20 mmol/L, 2 mmol/L and 10 The mmol/L NaOH aqueous solution is mixed in equal volume, stirring reaction 2 hours under room temperature condition, and 12000 revs/min centrifuge 30 minutes, And it is washed with water to neutrality.Finally it is placed in the drying 12 hours of 50 DEG C of thermostatic drying chamber, you can obtain the part of different reducing degrees Redox graphene solid（With pRGO1, pRGO2And pRGO3Represent the partial reduction graphite oxide of three kinds of different reducing degrees Alkene solid）.
Advantages of the present invention：
（1）Present invention composite part redox graphene under gentle chemical reaction condition.Preparation method green ring Protect, simple and efficient to handle, favorable reproducibility.
（2）The graphene oxide of partial reduction prepared by the present invention has larger sp2Hydridization region, less surface Defect and good dispersiveness and stability.
（3）The graphene oxide of partial reduction prepared by the present invention can be visited as high-efficiency fluorescence Resonance energy transfer nanometer Pin.
Brief description of the drawings
Fig. 1 is GO, pRGO1、pRGO2And pRGO3The outside drawing of the aqueous solution.
Fig. 2 is GO and pRGO3Atomic force microscopy diagram, in figure：A is GO, and b is pRGO3, the lamellar spacing song that c is GO Line, d is pRGO3Lamellar spacing curve.
Fig. 3 is GO, pRGO1、pRGO2And pRGO3X-ray diffractogram.
Fig. 4 is GO, pRGO1、pRGO2And pRGO3Raman spectrogram.
Fig. 5 is GO, pRGO1、pRGO2And pRGO3X-ray electron spectrum comparison figure, in figure：A is GO, and B is pRGO1, C is pRGO2, D is pRGO3。
Fig. 6 is GO, pRGO1、pRGO2、pRGO3After the ssDNA modified respectively with 6- Fluoresceincarboxylic acids is reacted at room temperature 30 seconds Fluorescence spectrum（The nm of excitation wavelength 494）.
Fig. 7 is the graph of a relation of fluorescent quenching rate and carbon-carbon bond ratio.
Embodiment
Example 1：
The g of 325 mesh crystalline flake graphite 2.7 is weighed, the concentrated sulfuric acid and 36 mL that 316 mL concentration are 18.4 mol/L is added to dense Spend in the mixed solution for 14.7 mol/L phosphoric acid.After being sufficiently stirred for, it is placed in 0 DEG C of ice bath.By 16.2 g potassium permanganate It is a small amount of multiple, it is slowly added into solution mixed above.0 DEG C of ice bath is kept, magnetic agitation is after 3 hours, by the blackish green suspension of gained Liquid is transferred in 35 DEG C of tepidariums, temperature control 1 hour, then the blackish green suspension of gained is transferred in 50 DEG C of tepidariums, temperature control 12 hours.360 mL frozen water are slowly added into obtained atropurpureus suspension, are stirred vigorously 1 hour.Then toward in solution by The wt % hydrogenperoxide steam generators of 12 mL 30 are added dropwise in drop, and solution colour sports glassy yellow, stirs 30 minutes.Resulting solution is through G1 Sand core funnel（Aperture 20-30 microns）Filtering, then 4000 rpms centrifuge 30 minutes, abandoning supernatant；Add 180 mL Distilled water fully vibrates washing, and 4000 rpms centrifuge 30 minutes, abandoning supernatant, and precipitation color is in khaki；Add The wt % hydrochloric acid of 180 mL 30 fully vibrates washing, through G1 sand core funnels（Aperture 20-30 microns）Filtering removes insoluble particles, filter 4000 rpms of liquid is centrifuged 30 minutes, abandoning supernatant, and precipitation color continues to deepen；Then repeatedly will be heavy with absolute ethyl alcohol It is neutrality that starch, which is washed till pH value, and 4000 rpms centrifuge 30 minutes, abandoning supernatant, and precipitation is in brown color；Finally use ether Precipitation is rinsed, through G5 sand core funnels（Aperture 1.5-2.5 microns）Filtering.Filter cake dries overnight at room temperature, obtains the oxygen of brown Graphite alkene.Take 400 mg graphite oxides to be dissolved in ultrasound 3 hours under 100 mL distilled waters, normal temperature, 4 are obtained after fully peeling off The brown color graphene oxide water solution of the transparent clarifications of mg/mL.
Example 2
The graphite oxide prepared by 10 mg embodiments 1 is taken to be dissolved in ultrasound 3 hours under 100 mL distilled waters, normal temperature, fully The brown color graphene oxide water solution of the transparent clarifications of 0.1 mg/mL is obtained after stripping（Fig. 1）.
Example 3
The GO aqueous solution prepared by 4 mg/mL embodiments 1 is mixed in equal volume with 20 μm of ol/L NaOH aqueous solution, in room Stirring reaction 2 hours under the conditions of temperature, 12000 revs/min centrifuge 30 minutes, and precipitation is washed with water to neutrality, 50 DEG C of dryings 12 Hour obtains the graphite oxide 1 of partial reduction（pRGO1）.Take 10 mg pRGO1It is dissolved in ultrasound 5 under 100 mL distilled waters, normal temperature Hour, the brown pRGO of the transparent clarifications of 0.1 mg/mL is obtained after fully peeling off1The aqueous solution（Fig. 1）.
Example 4
The GO aqueous solution prepared by 4 mg/mL embodiments 1 is mixed in equal volume with the 2 mmol/L NaOH aqueous solution, in room Stirring reaction 2 hours under the conditions of temperature, 12000 revs/min centrifuge 30 minutes, and precipitation is washed with water to neutrality, 50 DEG C of dryings 12 Hour obtains the graphite oxide 2 of partial reduction（pRGO2）.Take 10 mg pRGO2It is dissolved in ultrasound 5 under 100 mL distilled waters, normal temperature Hour, the brown pRGO of the transparent clarifications of 0.1 mg/mL is obtained after fully peeling off2The aqueous solution（Fig. 1）.
Example 5：
The GO aqueous solution prepared by 4 mg/mL embodiments 1 is mixed in equal volume with the 10 mmol/L NaOH aqueous solution, in room Stirring reaction 2 hours under the conditions of temperature, 12000 revs/min centrifuge 30 minutes, and precipitation is washed with water to neutrality, 50 DEG C of dryings 12 Hour obtains the graphite oxide 3 of partial reduction（pRGO3）.Take 10 mg pRGO1It is dissolved in ultrasound 5 under 100 mL distilled waters, normal temperature Hour, the brown pRGO of the transparent clarifications of 0.1 mg/mL is obtained after fully peeling off1The aqueous solution（Fig. 1）.
Example 6：
The mg/mL GO aqueous solution of 10 mL 3 and the mg/mL pRGO of 10 mL 3 are taken respectively3Water-soluble drop on mica sheet, Spontaneously dry overnight, with its size of atomic force microscope observation and lamellar spacing.As shown in Fig. 2 GO（A in Fig. 2）With pRGO3（B in Fig. 2）Size it is basically identical, in Fig. 2 c be GO lamellar spacing curve, d is pRGO3Lamellar spacing curve, GO and pRGO is understood by result3Lamellar spacing be 1.1 nm.
Example 7：
By obtained GO, pRGO1, pRGO2And pRGO3Carry out powder x-ray diffraction measure.As shown in figure 3, GO, pRGO1, pRGO2And pRGO32 (001) measured are 9.64 °, and 10.86 °, 10.98 °, and 11.10 °, 2 (002) are respectively 18.90 °, 22.10 °, 22.58 ° and 22.66 °.
Example 8：
By obtained GO, pRGO1, pRGO2And pRGO3Carry out Raman spectroscopy.Measure ID/IGRespectively 0.93, 0.89,0.90,0.86（Fig. 4）.Its ratio general status, which decreases, illustrates that reduction process makes graphene oxide segmental defect quilt Repair, orderly atomic arrangement region increase.
Example 9：
By obtained GO, pRGO1, pRGO2And pRGO3Carry out x-ray photoelectron power spectrum measure.As shown in Figure 5, with The enhancing of reducing degree, the oxygen-containing functional group of surface of graphene oxide is gradually decreased, and Csp2Hydridization region is gradually increased, C/O It is 0.49,0.51 and 0.53 that ratio is increased respectively by 0.46, and it is 34.22% that carbon-carbon bond ratio is increased respectively by 21.47%, 43.92%, and 52.46%.
Example 10：
15 μ L 100 μ g/mL GO, pRGO are taken respectively1、pRGO2、pRGO3, add 40 μ L500 nmol/L 6- carboxyls The ssDNA and the mmol/L pH 8.0 of 445 μ L 10 of fluorescein modification Tris-HCl buffer solutions（Containing 50 mmol/L NaCl With 1 mmol/L EDTA）, react at room temperature 30 seconds, fluorescence spectrum determined respectively（The nm of excitation wavelength 494）.From Fig. 6,7, portion Divide the Fluorescence quenching effect of redox graphene（Fluorescent quenching rate is 44.5 ~ 99.3%）It is better than graphene oxide（Fluorescent quenching Rate is 28.4%）, and strengthen with the increase fluorescent quenching of carbon-carbon bond ratio.
The exemplary embodiments of the present invention are the foregoing is only, are not intended to limit the invention, all essences in the present invention God and any modification made within principle, equivalent substitution and improvement etc., should be included in the scope of the protection.

Claims (7)

1. a kind of partial reduction graphene oxide FRET nano-probe, it is characterized in that：Partial reduction aoxidizes stone The lamellar spacing of black alkene FRET nano-probe is 1.1 nm, and 2 θ (001) are 10.86 ° ~ 11.10 °, 2 θ (002) it is 22.10 ° ~ 22.66 °, C/O ratios are 0.49 ~ 0.53, and carbon-carbon bond ratio is 34.22% ~ 52.46%, can be quenched fluorescence The fluorescence of molecular modification single stranded DNA；15 μ L concentration turn for 100 μ g/mL partial reduction graphene oxide fluorescence resonance energy Nano-probe is moved, 6- Fluoresceincarboxylic acid modification ssDNA and 445 μ L 10 mmol/ of the 40 μ L concentration for 500 nmol/L is added L, pH 8.0 Tris-HCl buffer solutions containing 50 mmol/L NaCl and 1 mmol/L EDTA, are reacted at room temperature 30 seconds, fluorescence Quenching rate is 44.5 ~ 99.3%；Used partial reduction graphene oxide is made by following steps：Graphene oxide is water-soluble Liquid is mixed in equal volume with the NaOH aqueous solution, after room temperature reaction, centrifugation washing, precipitates freeze-day with constant temperature, obtains partial reduction oxidation stone Black alkene solid, partial reduction graphene oxide solid is added water, and to peel off the partial reduction graphene oxide that must stablize water-soluble for ultrasound Liquid.
2. a kind of partial reduction graphene oxide FRET nano-probe according to claim 1, it is special Levying is：Fluorescence quenching effect strengthens with the increase of carbon-carbon bond ratio.
3. a kind of partial reduction graphene oxide FRET nano-probe according to claim 1, it is special Levying is：Used graphene oxide preparation method is：In the mixed solution that crystalline flake graphite is added to the concentrated sulfuric acid and phosphoric acid, fill Divide after stirring, be placed in 0 DEG C of ice bath, potassium permanganate is multiple on a small quantity, it is slowly added into solution mixed above, keeps 0 After DEG C ice bath, magnetic agitation, the blackish green suspension of gained is transferred in tepidarium and obtains blackish green suspension, it is then that gained is blackish green Suspension is transferred in tepidarium, and reaction obtains atropurpureus suspension, and frozen water is slowly added into obtained atropurpureus suspension In, acquisition solution is stirred vigorously, then toward hydrogenperoxide steam generator is added dropwise dropwise in solution, solution colour sports glassy yellow, stirs The G1 sand core funnels filtering of rear 20-30 microns of resulting solution via hole diameter is mixed, is then centrifuged, abandoning supernatant；In sediment Add distilled water and fully vibrate washing, centrifuge, abandoning supernatant, precipitation color is in khaki；Hydrochloric acid is added fully to shake Washing is swung, the G1 sand core funnels filtering of 20-30 microns of via hole diameter removes insoluble particles, and filtrate is centrifuged, and abandoning supernatant is sunk Shallow lake color continues to deepen；Then it is neutral sediment to be washed till into pH value with absolute ethyl alcohol, is centrifuged, abandoning supernatant, precipitation In brown color；Finally precipitated with washed with ether, the filtering of the G5 sand core funnels of 1.5-2.5 microns of via hole diameter, filter cake mistake at room temperature Night dries, and obtains the graphene oxide of brown.
4. a kind of partial reduction graphene oxide FRET nano-probe according to claim 1, it is special Levying is：The concentration of the NaOH aqueous solution is the mmol/L of 20 μm of ol/L ~ 10.
5. a kind of partial reduction graphene oxide FRET nano-probe according to claim 1, it is special Levying is：Reaction time is 0.5 ~ 2 hour.
6. a kind of partial reduction graphene oxide FRET nano-probe according to claim 1, it is special Levying is：Freeze-day with constant temperature temperature is 50 ~ 60 DEG C, and drying time is 6 ~ 12 hours.
7. a kind of partial reduction graphene oxide FRET nano-probe according to claim 3, it is special Levying is：Used graphene oxide preparation method is：The g of 325 mesh crystalline flake graphite 2.7 is weighed, being added to 316 mL concentration is In the mixed solution of the 18.4 mol/L concentrated sulfuric acid and 36 mL concentration for 14.7 mol/L phosphoric acid, after being sufficiently stirred for, it is placed at It is in 0 DEG C of ice bath, 16.2 g potassium permanganate are multiple on a small quantity, it is slowly added into solution mixed above, keeps 0 DEG C of ice bath, magnetic After power is stirred 3 hours, the blackish green suspension of gained is transferred in 35 DEG C of tepidariums, temperature control 1 hour, it is then that gained is blackish green mixed Suspension is transferred in 50 DEG C of tepidariums, temperature control 12 hours, and 360 mL frozen water are slowly added into obtained atropurpureus suspension mixing In thing, 1 hour is stirred vigorously, then toward 12 mL 30wt% hydrogenperoxide steam generators, solution colour mutation are added dropwise dropwise in solution For glassy yellow, stir 30 minutes, the G1 sand core funnels filtering of 20-30 microns of resulting solution via hole diameter, then 4000 revolutions per minute Zhongli's heart 30 minutes, abandoning supernatant；Add 180 mL distilled waters and fully vibrate washing, 4000 rpms centrifuge 30 points Clock, abandoning supernatant, precipitation color is in khaki；Add 180 mL 30wt% hydrochloric acid and fully vibrate washing, via hole diameter 20-30 The G1 sand core funnels filtering of micron removes insoluble particles, and 4000 rpms of filtrate centrifuges 30 minutes, abandoning supernatant, precipitation Color continues to deepen；Then it is neutral sediment repeatedly to be washed till into pH value with absolute ethyl alcohol, and 4000 rpms centrifuge 30 points Clock, abandoning supernatant, precipitation is in brown color；Finally precipitated with washed with ether, the G5 sand core funnel mistakes of 1.5-2.5 microns of via hole diameter Filter, filter cake dries overnight at room temperature, obtains the graphene oxide of brown.
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CN104240960B (en) * 2014-10-09 2017-12-15 哈尔滨工业大学 High density ordered graphene with ion wall and its preparation method and application

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