CN109939665A - Graphite oxide alkynes nanometer sheet of photodissociation aquatic products oxygen and preparation method thereof and application under a kind of visible light - Google Patents
Graphite oxide alkynes nanometer sheet of photodissociation aquatic products oxygen and preparation method thereof and application under a kind of visible light Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of the graphite oxide alkynes nanometer sheet of photodissociation aquatic products oxygen under visible light, the method provided by the invention for preparing graphite oxide alkynes nanometer sheet is simple, efficiently, low in cost.The graphite oxide alkynes nanometer sheet surface that the present invention is prepared has oxygen-containing functional group abundant, there is fabulous dispersibility in water, be conducive to improve light absorption, the graphite oxide alkynes nanometer sheet possesses uniform size and ultra-thin thickness, be conducive to the separation and transmission of light induced electron, hole, improve the performance of photodissociation aquatic products oxygen under visible light.Graphite oxide alkynes nanometer sheet material prepared by the present invention has preferable absorption in visible-range, and band structure meets the requirement that water decomposition generation oxygen is catalyzed under radiation of visible light, realizes high-performance visible light solution aquatic products oxygen.Also, graphite oxide alkynes nanometer sheet material prepared by the present invention still shows excellent photodissociation aquatic products oxygen performance under near infrared light (λ=660nm) irradiation.
Description
Technical field
The invention belongs to photocatalytic water oxygen technical fields, and in particular to the oxidation stone of photodissociation aquatic products oxygen under a kind of visible light
Black alkynes nanometer sheet and preparation method thereof.
Background technique
It is the high effective way for converting solar energy into chemical energy using semiconductor catalyst photocatalytic water splitting, limits at present
The biggest obstacle of photocatalytic water splitting is water oxygen half-reaction, and water oxygen metaplasia needs to shift multiple electronics and higher at oxygen
Overpotential is the process of dynamics lag.Therefore seek efficient, the cheap novel visible solution aquatic products oxygen of one kind to urge
Agent is always the hot spot and emphasis of the research field.
Existing visible photodissociation aquatic products VPO catalysts are mainly the metals based semiconductor such as silver orthophosphate, pucherite, iron oxide, these
Although material produces oxygen field in visible light catalytic water decomposition and has carried out compared with in-depth study, since their band gap regulate and control
It is difficult, it usually needs to construct hetero-junctions with other semiconductors couplings to obtain preferable performance, while the based semiconductor contains gold
Belong to the synthesis cost for increasing catalyst, is unfavorable for industrial application.Another kind of is the organic semiconductor based on carbonitride, this kind of half
Conductor synthesis cost is cheap, and band gap is controllable, but since water oxidation kinetics lags, catalytic activity is very low, it is therefore desirable to
The co-catalysts such as ruthenium-oxide, yttrium oxide, cobaltosic oxide are added, industrial application is equally unfavorable for.
Graphite alkene is one kind by sp and sp2The New Two Dimensional organic semiconductor that hydbridized carbon atoms collectively constitute, due to its
There is preferable absorb under visible light and be successfully applied to photocatalysis related fields.German " advanced energy and material "
(Advanced Energy Materials, 2018 volume 8 page 1702992), which is reported, is grown in stone for carbon nitride material
The surface of black alkynes constitutes two-dimensional hetero-junction and improves its hydrogen-producing speed using the high hole transfer ability of graphite alkene material.It is this multiple
It is complicated to close catalyst preparation process, and in order to improve performance, deposited Pt nanoparticle on its surface, be unfavorable for answering on a large scale
With.
Therefore, compound without using other co-catalysts or semiconductor and graphite alkene, and merely by modify functional group or
The approach for changing skeleton composition adjusts the bandgap structure of graphite alkene, and is further applied to visible photodissociation aquatic products oxygen at present still
It is not studied.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of oxidation stone of photodissociation aquatic products oxygen under visible light
Black alkynes nanometer sheet and preparation method thereof, the present invention modifies oxygen-containing functional group to graphite alkene by oxidation and the removing of liquid phase ultrasound changes
Become its thickness, the common band gap for adjusting graphite alkene realizes graphite in the case where being not introduced into other any metals or semiconductor
The adjusting of alkynes band structure improves the performance of photodissociation aquatic products oxygen under visible light.
The present invention provides a kind of preparation methods of the graphite oxide alkynes nanometer sheet of photodissociation aquatic products oxygen under visible light, including with
Lower step:
A) graphite alkene is aoxidized using mixed strong acids, obtains graphite oxide alkynes；
B) the graphite oxide alkynes is removed using the removing of liquid phase ultrasound, after centrifuge separation, obtains graphite oxide alkynes nanometer
Piece.
Preferably, the mixed strong acids are selected from the mixed acid of the concentrated sulfuric acid and concentrated nitric acid, the body of the concentrated sulfuric acid and concentrated nitric acid
Product is than being 1:2~2:5.
Preferably, step A) specifically:
Under conditions of 0 DEG C, graphite alkene is added into mixed strong acids, mixture is obtained；
The mixture is subjected to oxidation reaction under conditions of 25 ± 5 DEG C, obtains graphite oxide alkynes.
Preferably, the graphite alkene and the mass volume ratio of mixed strong acids are 50mg:15ml~60mg:15ml.
Preferably, the liquid phase dispersion liquid that the liquid phase ultrasound removing uses is the mixed liquor of deionized water and concentrated hydrochloric acid, institute
The volume ratio for stating deionized water and concentrated hydrochloric acid is 40ml:0.05ml~40ml:0.06ml.
Preferably, the mass volume ratio of the graphite oxide alkynes and liquid phase dispersion liquid is 10mg:40.05ml~15mg:
40.05ml。
Preferably, the temperature of the ultrasonic treatment is 5~20 DEG C；The ultrasonic power of ultrasonic treatment is 100~200W；Ultrasound
The supersonic frequency of processing is 20~60KHz；The time of ultrasonic treatment is 20~30h.
Preferably, the centrifuge separation condition are as follows: by the dispersion liquid after graphite oxide alkynes removing with 3000 ±
The revolving speed of 100rpm is centrifugated 5 ± 0.5 minutes, is removed sediment, is obtained upper layer dispersion liquid；
The upper layer dispersion liquid is centrifuged 10 ± 1 minutes using the revolving speed of 8000 ± 500rpm, sediment is collected, obtains oxygen
Graphite alkynes nanometer sheet.
The present invention also provides a kind of graphite oxides of photodissociation aquatic products oxygen under visible light that above-mentioned preparation method is prepared
Alkynes nanometer sheet, the graphite oxide alkynes nanometer sheet with a thickness of 1.7 ± 0.1nm, the graphite oxide alkynes nanometer sheet lamella size
For 120 ± 10nm.
The present invention also provides a kind of applications of above-mentioned graphite oxide alkynes nanometer sheet photodissociation aquatic products oxygen under visible light.
Compared with prior art, the present invention provides the graphite oxide alkynes nanometer sheets of photodissociation aquatic products oxygen under a kind of visible light
Preparation method, comprising the following steps: A) graphite alkene is aoxidized using mixed strong acids, obtain graphite oxide alkynes；B) super using liquid phase
The graphite oxide alkynes is removed in sound removing, after centrifuge separation, obtains graphite oxide alkynes nanometer sheet.The present invention is by oxidation to stone
Black alkynes carries out oxygen-containing functional group modification and the removing of liquid phase ultrasound changes its thickness, and the common band gap for adjusting graphite alkene is not being drawn
In the case where entering other any metals or semiconductor, the adjusting of graphite alkene band structure is realized.It is provided by the invention to prepare oxygen
The method of graphite alkynes nanometer sheet is simple, efficiently, low in cost.The graphite oxide alkynes nanometer sheet surface tool that the present invention is prepared
There is oxygen-containing functional group abundant, there is fabulous dispersibility in water, is conducive to improve light absorption, the graphite oxide alkynes nanometer sheet
Possess uniform size and ultra-thin thickness, be conducive to the separation and transmission of light induced electron, hole, improves photocatalytic water under visible light
Produce the performance of oxygen.Graphite oxide alkynes nanometer sheet material prepared by the present invention has preferable absorption, Er Qieneng in visible-range
Band structure, which meets, is catalyzed the requirement that water decomposition generates oxygen under radiation of visible light, realize high-performance visible light solution aquatic products oxygen.And
And graphite oxide alkynes nanometer sheet material prepared by the present invention is still shown excellent under near infrared light (λ=660nm) irradiation
Photodissociation aquatic products oxygen performance.
Detailed description of the invention
Fig. 1 is the molecular structural formula and graphite alkene and oxygen of graphite oxide alkynes nanometer sheet prepared by the embodiment of the present invention 1,2,3
The Raman spectrum analysis of graphite alkynes nanometer sheet；
Fig. 2 is the x-ray photoelectron spectroscopy of graphite alkene prepared by the embodiment of the present invention 1,2,3 and graphite oxide alkynes nanometer sheet
Analysis；
Fig. 3 is the transmission electron microscope figure and scanning electron microscope diagram for the graphite alkene that the embodiment of the present invention 1 is prepared；
Fig. 4 is transmission electron microscope figure, the atomic force for the graphite oxide alkynes nanometer sheet that the embodiment of the present invention 2,3 is prepared
Microscope and its thickness chart；
Fig. 5 be the graphite alkene that the embodiment of the present invention 1 is prepared the diffusing reflection of UV, visible light near infrared light and corresponding optics
Band gap diagram；
Fig. 6 is the UV, visible light near infrared light diffusing reflection for the graphite oxide alkynes nanometer sheet that the embodiment of the present invention 2,3 is prepared
And corresponding optical band gap figure；
Fig. 7 is the visible photodissociation aquatic products oxygen performance map of Application Example graphite alkene of the present invention Yu graphite oxide alkynes nanometer sheet.
Specific embodiment
The present invention provides a kind of preparation methods of the graphite oxide alkynes nanometer sheet of photodissociation aquatic products oxygen under visible light, including with
Lower step:
A) graphite alkene is aoxidized using mixed strong acids, obtains graphite oxide alkynes；
B) the graphite oxide alkynes is removed using the removing of liquid phase ultrasound, after centrifuge separation, obtains graphite oxide alkynes nanometer
Piece.
The present invention carries out the preparation of graphite oxide alkynes nanometer sheet using graphite alkene as raw material, wherein the graphite alkene is according to such as
It is prepared by lower method:
The acetone soln of six alkynyl benzene is added molten to acetone, pyridine and the tetramethylethylenediamine mixing for having dispersed copper sheet
It in liquid, and uses nitrogen as gas is protected, is reacted under heating condition, obtain graphite alkene.
The concentration of six alkynyl benzene is 0.8mg/ml~1.0mg/ml in the acetone soln of six alkynyl benzene.
The acetone soln of the six alkynyls benzene and the volume ratio of mixed solution are 45ml:106ml~50ml:106ml.
The volume ratio of the acetone, pyridine and tetramethylethylenediamine is (100 ± 1): (5 ± 0.05): (1 ±
0.01)。
The amount that the copper sheet is added in the mixed solution is (50 ± 5) mg:(106 ± 1) ml.
The temperature of the reaction is 50 DEG C, and the time of the reaction is 24 hours.
Then, the graphite alkene is aoxidized using mixed strong acids, obtains graphite oxide alkynes.
Wherein, the mixed strong acids are selected from the mixed acid of the concentrated sulfuric acid and concentrated nitric acid, the volume of the concentrated sulfuric acid and concentrated nitric acid
Than for 1:2~2:5.
Specifically, the step of preparing graphite oxide alkynes nanometer sheet are as follows:
Under conditions of 0 DEG C, graphite alkene is added into mixed strong acids, obtains mixture, the graphite alkene with mix it is strong
The mass volume ratio of acid is 50mg:15ml~60mg:15ml.
The mixture is subjected to oxidation reaction under conditions of 25 ± 5 DEG C, wherein the time of oxidation reaction is 6~8 small
When.
After the reaction solution of oxidation reaction is diluted with deionized water, makes to be washed with deionized, is centrifuged acquisition graphite oxide
Alkynes.
Then, it is removed using liquid phase ultrasound and removes the graphite oxide alkynes, after centrifuge separation, obtained graphite oxide alkynes and receive
Rice piece.
Wherein, the liquid phase dispersion liquid that the liquid phase ultrasound removing uses is described for the mixed liquor of deionized water and concentrated hydrochloric acid
Deionized water and the volume ratio of concentrated hydrochloric acid are 40ml:0.05ml~40ml:0.06ml.
Specifically, it disperses graphite oxide alkynes in liquid phase dispersion liquid, dispersion liquid is then placed in ultrasound in ultrasonic machine and is shelled
From.The mass volume ratio of the graphite oxide alkynes and liquid phase dispersion liquid is 10mg:40.05ml~15mg:40.05ml.
The temperature of the ultrasonic treatment is 5~20 DEG C, preferably 10~15 DEG C；The ultrasonic power of ultrasonic treatment be 100~
200W, preferably 130~170W；The supersonic frequency of ultrasonic treatment is 20~60KHz, preferably 30~50KHz；Ultrasonic treatment
Time is 20~30h, preferably 24~28h.
After ultrasound removing, unstripped raw material is separated with the graphite oxide alkynes nanometer sheet of removing using centrifugation.Described
Centrifuge separation condition are as follows: by the dispersion liquid after graphite oxide alkynes removing with the revolving speed of 3000 ± 100rpm centrifuge separation 5 ±
0.5 minute, sediment is removed, upper layer dispersion liquid is obtained.
The upper layer dispersion liquid is centrifuged 10 ± 1 minutes using the revolving speed of 8000 ± 500rpm, sediment is collected, obtains oxygen
Graphite alkynes nanometer sheet.
The present invention also provides a kind of graphite oxide alkynes nanometer sheet that above-mentioned preparation method is prepared, the graphite oxides
The thickness of alkynes nanometer sheet is uniform, is 1.7 ± 0.1nm, and the graphite oxide alkynes nanometer sheet lamella size is uniform, is 120 ± 10nm.
The present invention also provides a kind of applications of above-mentioned graphite oxide alkynes nanometer sheet photodissociation aquatic products oxygen under visible light.This hair
The graphite oxide alkynes nanometer sheet of bright offer realizes visible photodissociation aquatic products oxygen and near infrared light (λ=660nm) solution aquatic products oxygen.It will
Resulting material is successfully applied to high-performance photodissociation aquatic products oxygen under visible light, unit oxygen-producing amount as organic semiconductor photochemical catalyst
Up to 150.7 μm of ol/g/h.
Graphite oxide alkynes nanometer sheet provided by the invention has uniform size and ultra-thin thickness, is conducive to photoproduction electricity
The separation and transmission of son, hole, and then improve the performance of photodissociation aquatic products oxygen under visible light；Graphite oxide alkynes prepared by the present invention is received
Rice sheet material has preferable absorption in visible-range, and band structure meets catalysis water decomposition under radiation of visible light and generates
The requirement of oxygen realizes high-performance visible light solution aquatic products oxygen.
Photodissociation aquatic products oxygen is that graphite oxide alkynes nanometer sheet obtained is dispersed in deionized water and electronics under the visible light
In the solution of sacrifice agent, solution is transferred in transparent quartz container, leads to argon gas and exclude the sealing of air blend rubber plug, then
It is greater than the light source of 420nm with wavelength at room temperature to irradiate, and calculates the amount for generating oxygen with gas chromatographic detection.
Compared with prior art the invention has the following advantages that
1. the method for preparing graphite oxide alkynes nanometer sheet is simple, efficiently, low in cost；
2. carrying out oxygen-containing functional group modification to graphite alkene by oxidation and ultrasound removing changing its thickness, stone is adjusted jointly
The band gap of black alkynes realizes the adjusting of graphite alkene band structure in the case where being not introduced into other any metals or semiconductor；
3. the graphite oxide alkynes nanometer sheet surface being prepared has oxygen-containing functional group abundant, have in water fabulous
Dispersibility is conducive to improve light absorption；
4. the graphite oxide alkynes nanometer sheet being prepared possesses uniform size and ultra-thin thickness, be conducive to photoproduction electricity
The separation and transmission of son, hole improve the performance of photodissociation aquatic products oxygen under visible light；
5. graphite oxide alkynes nanometer sheet material prepared by the present invention has preferable absorption, and energy band in visible-range
Structure, which meets, is catalyzed the requirement that water decomposition generates oxygen under radiation of visible light, realize high-performance visible light solution aquatic products oxygen；
6. graphite oxide alkynes nanometer sheet material prepared by the present invention is still shown under near infrared light (λ=660nm) irradiation
Excellent photodissociation aquatic products oxygen performance.
For a further understanding of the present invention, below with reference to embodiment to photodissociation aquatic products oxygen under visible light provided by the invention
Graphite oxide alkynes nanometer sheet and preparation method thereof and application are illustrated, and protection scope of the present invention is not by following embodiment
Limitation.
Embodiment 1:
100 milliliters of acetone, 5 milliliters of pyridine and 1 milliliter of tetramethylethylenediamine are mixedly configured into solution, are added
The clean copper sheet of 50mg, then under nitrogen atmosphere protection, by the acetone for the six alkynyl benzene that 50 milliliters of concentration are 1 mg/ml
Solution injects above-mentioned solution using syringe pump with 25 mls/hour of speed.The mixed system is protected in 50 DEG C of oil baths, nitrogen atmosphere
Shield lower reaction 24 hours.Finally successively using the acetone of heat, pyridine, the abundant washing sample of n,N-Dimethylformamide, removing is not
The monomer and oligomer of reaction obtain graphite alkene sample.
Embodiment 2:
At 0 DEG C, 5 milliliters of concentrated sulfuric acids are mixed with 10 milliliters of concentrated nitric acids, then slowly add 50 milligrams of graphite alkene sample
Enter mixed liquor.Room temperature magnetic agitation is reacted 6 hours.The dispersion liquid is diluted using 200 ml deionized waters, sample is collected by centrifugation,
And thoroughly being washed using deionized water to separating liquid pH value is neutrality, room temperature in vacuo is dry, obtains graphite oxide alkynes sample.
Embodiment 3:
By in 10 milligrams of graphite oxide alkynes sample dispersion to 40 ml deionized waters and 0.05 milliliter of hydrochloric acid mixed solution,
Dispersion liquid is placed in ultrasonic machine again and carries out the removing of liquid phase ultrasound (ultrasonic machine power is 150 watts, and frequency is 40 kHz), temperature
10 DEG C are maintained at hereinafter, ultrasound removing 24 hours.Dispersion liquid is centrifugated 5 minutes with the revolving speed of 3000rpm, is made unstripped
With the sample pellet assembled after removing.Upper layer dispersion liquid is centrifuged 10 minutes again using the revolving speed of 8000rpm finally, is obtained ultra-thin
Graphite oxide alkynes nanometer sheet.
Attached drawing 1a is the molecular structural formula for the graphite oxide alkynes nanometer sheet that embodiment 1,2,3 is prepared；
Attached drawing 1b is the Raman spectrum analysis of the graphite alkene that embodiment 1,2,3 is prepared and graphite oxide alkynes nanometer sheet, stone
Black alkynes is expressed as GDY, and graphite oxide alkynes nanometer sheet is expressed as GDYO.It can be seen that graphite alkene exists after oxidation, lift-off processing
1920cm-1With 2178cm-1The characteristic peak at place weakens, and illustrates that the conjugated structure of graphite oxide alkynes nanometer sheet is conditioned；
Attached drawing 2a is the X-ray photoelectron spectroscopic analysis for the graphite alkene that embodiment 1 is prepared, and the content of sp hydridization carbon is
sp2Twice of hydridization carbon illustrates that graphite alkene is successfully passed through embodiment 1 and synthesized；
Attached drawing 2b is the X-ray photoelectron spectroscopic analysis for the graphite oxide alkynes nanometer sheet that embodiment 2,3 is prepared, sp hydridization
The content of carbon substantially reduces, and illustrates that the conjugated structure of graphite alkene is conditioned, and the content of C-O and C=O significantly increase, and illustrate graphite
Alkynes is successfully aoxidized；
Attached drawing 3a, b are the transmission electron microscope figure and scanning electron microscope diagram for the graphite alkene that embodiment 1 obtains, figure
It is upper it can be seen that graphite alkene stacked in multi-layers, forms the aggregation of flower shape, this is because its have between layers it is very strong
It is conjugated interaction force；
Attached drawing 4a, b are that the transmission electron microscope figure for the graphite oxide alkynes nanometer sheet that embodiment 2,3 obtains, atomic force are aobvious
Micro mirror and its thickness chart, the size of graphite oxide alkynes nanometer sheet is 120 ± 10 nanometers, with a thickness of 1.7 ± 0.1 nanometers；
Attached drawing 5a, b are the UV, visible light near infrared light diffusing reflection figure and optical band gap figure for the graphite alkene that embodiment 1 obtains,
Illustrate that obtaining sample has preferable absorb in visible light region；Optical band gap is 1.46eV；
Attached drawing 6a, b be the graphite oxide alkynes nanometer sheet that embodiment 2,3 obtains UV, visible light near infrared light diffusing reflection figure with
Optical band gap figure illustrates that obtaining sample has preferable absorb in visible light region；Optical band gap is 1.64eV, illustrates its band gap
It is conditioned, has the ability used as visible light catalyst.
Application Example: photodissociation aquatic products oxygen under visible light
10 milligrams of materials being prepared are added into sealable quartzy bottle, add 50 ml deionized waters and 84.9
Milligram silver nitrate, ultrasonic disperse are handled 15 minutes.Being bubbled with 0.1 liter/min of flow velocity into dispersion liquid with argon gas 30 minutes will
Air in solvent and container excludes completely, then to be sealed container with rubber stopper and sealed membrane.And container is placed on intensity
For under 100 milliwatts/square centimeter light source, light source is provided by xenon lamp, and placing at light source transmitting only allows wavelength to be greater than
The optical filter that 420nm light penetrates.Entire photodissociation aquatic products oxygen test temperature maintains 25 ± 5 DEG C.
Every 1 hour, 1 milliliter of gas is extracted from quartzy bottle with syringe, and detected with gas chromatograph and calculate gas
The content of middle oxygen the total output of oxygen can be obtained multiplied by the total volume of gas in quartzy bottle, by total output divided by institute's used time
Between and the quality of material therefor the unit oxygen-producing amount of material can be calculated.
If other conditions of the present embodiment are constant, change the laser light source that xenon source is wavelength 660nm, it can test waves
Photodissociation aquatic products oxygen performance under long 660nm light source irradiation.
Attached drawing 7 is graphite oxide alkynes nanometer sheet, graphite alkene the photodissociation aquatic products under different wavelength range in this application embodiment
Oxygen performance map.Graphite oxide alkynes nanometer sheet unit produces oxygen rate and reaches 150.7 μm of ol/g/h (λ > 420nm) or 50.3 μm of ol/g/h
(λ=660nm)；Graphite alkene unit produces oxygen rate and reaches 4.8 μm of ol/g/h (λ > 420nm).
Embodiment 4
According to the preparation method of Examples 1 to 3, only changes the technique when removing of liquid phase ultrasound, do not use low-speed centrifugal
(3000 ± 100rpm, 5 ± 0.5min) separates the graphite oxide alkynes of different extent of exfoliation, is directly turned using 8000 ± 500rpm
10 ± 1min of speed centrifugation obtains mixing sample, is applied to visible light catalytic water decomposition and produces oxygen, unit produces oxygen rate and reaches 78.2 μ
Mol/g/h, this is because the unstripped sample in part, which reduces unit, produces oxygen rate.
Embodiment 5
According to the preparation method of Examples 1 to 3, only change the technique when removing of liquid phase ultrasound, shortens ultrasonic splitting time
To 12h, it is 65.8 μm of ol/g/h that the visible light catalytic unit of the graphite oxide alkynes nanometer sheet obtained after centrifuge separation, which produces oxygen rate,
This is because ultrasonic splitting time is shorter, sample is thicker for 24 hours for isolated graphite oxide alkynes nanometer sheet thickness distribution relatively removing,
It is reduced to which unit produces oxygen rate.
Embodiment 6
According to the preparation method of Examples 1 to 3, only change the technique when removing of liquid phase ultrasound, extends ultrasonic splitting time
To 36h, it is 83.2 μm of ol/g/h that the visible light catalytic unit of the graphite oxide alkynes nanometer sheet obtained after centrifuge separation, which produces oxygen rate,
This is because ultrasonic splitting time is too long, the conjugated structure of graphite oxide alkynes nanometer sheet destroys serious, reduces it to can be by light
Absorption, unit produce oxygen rate reduce.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. the preparation method of the graphite oxide alkynes nanometer sheet of photodissociation aquatic products oxygen under a kind of visible light, which is characterized in that including following
Step:
A) graphite alkene is aoxidized using mixed strong acids, obtains graphite oxide alkynes；
B) the graphite oxide alkynes is removed using the removing of liquid phase ultrasound, after centrifuge separation, obtains graphite oxide alkynes nanometer sheet.
2. preparation method according to claim 1, which is characterized in that the mixed strong acids are selected from the concentrated sulfuric acid and concentrated nitric acid
The volume ratio of mixed acid, the concentrated sulfuric acid and concentrated nitric acid is 1:2~2:5.
3. preparation method according to claim 1, which is characterized in that step A) specifically:
Under conditions of 0 DEG C, graphite alkene is added into mixed strong acids, mixture is obtained；
The mixture is subjected to oxidation reaction under conditions of 25 ± 5 DEG C, obtains graphite oxide alkynes.
4. preparation method according to claim 3, which is characterized in that the mass volume ratio of the graphite alkene and mixed strong acids
For 50mg:15ml~60mg:15ml.
5. preparation method according to claim 1, which is characterized in that the liquid phase dispersion liquid that the liquid phase ultrasound removing uses
For the mixed liquor of deionized water and concentrated hydrochloric acid, the volume ratio of the deionized water and concentrated hydrochloric acid is 40ml:0.05ml~40ml:
0.06ml。
6. preparation method according to claim 5, which is characterized in that the quality of the graphite oxide alkynes and liquid phase dispersion liquid
Volume ratio is 10mg:40.05ml~15mg:40.05ml.
7. preparation method according to claim 1, which is characterized in that the temperature of the ultrasonic treatment is 5~20 DEG C；Ultrasound
The ultrasonic power of processing is 100~200W；The supersonic frequency of ultrasonic treatment is 20~60KHz；The time of ultrasonic treatment be 20~
30h。
8. preparation method according to claim 1, which is characterized in that the centrifuge separation condition are as follows: by the oxidation
Dispersion liquid after graphite alkene removing is centrifugated 5 ± 0.5 minutes with the revolving speed of 3000 ± 100rpm, is removed sediment, is obtained
Layer dispersion liquid；
The upper layer dispersion liquid is centrifuged 10 ± 1 minutes using the revolving speed of 8000 ± 500rpm, sediment is collected, obtains oxidation stone
Black alkynes nanometer sheet.
9. the oxidation of photodissociation aquatic products oxygen under a kind of visible light that the preparation method such as claim 1~8 any one is prepared
Graphite alkene nanometer sheet, the graphite oxide alkynes nanometer sheet with a thickness of 1.7 ± 0.1nm, the graphite oxide alkynes nanometer sheet lamella
Having a size of 120 ± 10nm.
10. a kind of application of graphite oxide alkynes nanometer sheet as claimed in claim 9 photodissociation aquatic products oxygen under visible light.
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| CN110668436A (en) * | 2019-11-04 | 2020-01-10 | 北京科技大学 | Preparation method of ultrathin nanoscale graphite alkyne film |
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