CN109331804A - A kind of graphene nano disk and its preparation method and application - Google Patents
A kind of graphene nano disk and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 56
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000019253 formic acid Nutrition 0.000 claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000000502 dialysis Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002356 single layer Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000009938 salting Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 210000001550 testis Anatomy 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Abstract
The present invention relates to a kind of nano materials, and in particular to a kind of size it is controllable, the graphene nano disk that pattern is uniform and its preparation method and application.The simple one step hydro thermal method of first passage of the present invention prepares the single-layer graphene nanometer plate that size is controllable, pattern is uniform, is a kind of carbon-based material rich in oxygen defect of low cost, has excellent CO2Catalytic reduction performance.In overpotential 430mV, it is catalyzed CO2The faradic efficiency for generating formic acid can reach 87%, originate overpotential down to 230mV, and without other by-products, improve the problems that carbon-supported catalysts face, this is also the carbon-based material catalysis reduction CO reported at present2Generate the top performance of formic acid.The preparation method of graphene nano disk provided by the invention, raw material is easy to get and process flow is simple, greatly reduces production cost, is conducive to large-scale industrialization application；And electrolyte is all common common salting liquid, does not add any organic matter.
Description
Technical field
The present invention relates to a kind of nano materials, and in particular to a kind of graphene nano disk that size is controllable, pattern is uniform
And its preparation method and application.
Background technique
Since the industrial revolution, along with the made rapid progress of human production life, more and more carbon dioxide are discharged
It has arrived in atmosphere.The carbon dioxide of the discharge of this sustainable growth, which has begun, gradually impacts earth environment.In addition,
CO2Global warming caused by a large amount of discharges has become one of most concerned environmental issue in the whole world.Therefore, efficiently by greenhouse gas
Body CO2Being converted to the liquid fuel with added value extremely has researching value.Due to mild reaction condition and reaction product
Modulatory character, electro-catalysis restore carbon dioxide (CO2It RR) is the small molecule product for having economic value, it has also become increasing the energy needs
Seek promising solution.Through research and development in a few years, although researchers have developed a large amount of efficient electro-catalysis
Agent restores CO for electro-catalysis2, but how to realize while meeting actual production demand, reducing catalyst preparation cost still
Being able to maintain higher catalytic efficiency is always the Research Challenges in field.
Electrochemical carbon dioxide reduction process is also faced with numerous challenges, most important of which is that how to improve reaction efficiency
And selectivity of product, this needs to rationally design catalyst to realize efficient and highly selective carbon dioxide reduction reaction.Formic acid
It can be made into due to its high-energy density, convenient for long-distance transport and directly a kind of very promising as reproducible transport fuel
Aminic acid fuel battery the characteristics of, the extensive concern by researcher.However, that is reported at present is converted to for carbon dioxide
The catalysis agent producing process of formic acid is complicated, cost of material is expensive, mainly based on metallic catalyst；And it is converted into formic acid
Efficiency it is lower, required overpotential is higher.
Summary of the invention
The invention solves in the prior art the technical issues of, a kind of graphene that size is controllable, that pattern is uniform is provided
Nanometer plate and its preparation method and application.Graphene nano disk of the invention is a kind of carbon-based material rich in oxygen defect, is used for
(430mV) catalysis reduction CO under lower overpotential2Formic acid is generated, faradic efficiency reaches 87%, and preparation process is extremely
Simply, production cost is greatly reduced, large-scale industrialization application is conducive to.
In order to solve the above-mentioned technical problem, technical solution of the present invention is specific as follows:
The present invention provides a kind of preparation method of graphene nano disk, comprising the following steps:
Using graphene oxide powder as raw material, using concentrated nitric acid as solvent, graphene nano disk is made by hydro-thermal method.
In the above-mentioned technical solutions, the graphene oxide powder is prepared by the following method:
Natural graphite 1g is weighed, 0.74g NaNO is added3With 34mL 98%H2SO4, mix in ice-water bath, acutely stir
It mixes；It is slowly added to 5g KMnO later4, keep temperature to be lower than 20 DEG C, be then transferred to 35 DEG C of stirred in water bath 3 hours；Stirring
After be added 250mL deionized water, be slowly added to 4mL 30%wt H2O2Reaction was completed；Obtained glassy yellow suspension is first
With 5% hydrochloric acid solution centrifuge washing, to remove remaining H2SO4, then repeatedly cleaned with deionized water until pH is in neutrality；It will
Graphene solution after having washed is dried to obtain solid powder by freeze-drying or vacuum drying mode.
In the above-mentioned technical solutions, the mass fraction of the concentrated nitric acid is 65%.
In the above-mentioned technical solutions, the preparation method specific steps of the graphene nano disk include:
Dried graphene oxide powder is weighed, the concentrated nitric acid that mass fraction is 65% is added, the concentrated nitric acid adds
Enter volume is graphene oxide powder quality 1/10~1/20, ultrasonic agitation is until form evenly dispersed solution, Zhi Houfang
It sets in hydrothermal reaction kettle, is reacted 4~10 hours at 100-200 DEG C, after reaction kettle is cooled to room temperature, steamed using rotation
Hair, centrifugation and the mode dialysed repeatedly are added distillation water washing, collect, drying, obtain stone that size is controllable, that pattern is uniform
Black alkene nanometer plate.
In the above-mentioned technical solutions, the dosage of the graphene oxide powder is 400mg, and the dosage of concentrated nitric acid is 20-
40mL。
In the above-mentioned technical solutions, reaction temperature is 140-180 DEG C.
In the above-mentioned technical solutions, reaction temperature is 160 DEG C, and the time is 6 hours.
The present invention also provides a kind of graphene nano disks of above-mentioned preparation method preparation.
In the above-mentioned technical solutions, the size of the graphene nano disk is 30nm~180nm, with a thickness of 1nm；And it aoxidizes
Degree g value reaches 2.01.
The present invention also provides a kind of graphene nano disks of above-mentioned preparation method preparation to restore dioxy for efficient electro-catalysis
Change the application that carbon generates formic acid.
The beneficial effects of the present invention are:
1, electro-catalysis well known in the prior art restores CO2Most of the catalyst for generating formic acid is metal and its alloying
Material, expensive starting materials, preparation process are complicated；And seldom have been reported that carbon-based material itself can be catalyzed reduction CO2.The present invention is led to for the first time
It crosses simple one step hydro thermal method and prepares the single-layer graphene nanometer plate that size is controllable, pattern is uniform, be a kind of low cost
Carbon-based material rich in oxygen defect has excellent CO2Catalytic reduction performance.
2, graphene nano disk provided by the invention is as catalyst for being catalyzed reduction CO2Formic acid is generated, in overpotential
In the case of 430mV, it is catalyzed CO2The faradic efficiency for generating formic acid can reach 87%, originate overpotential down to 230mV, and do not have
Other by-products improve the problems that carbon-supported catalysts face, this is also the carbon-based material catalysis reduction reported at present
CO2Generate the top performance of formic acid.The present invention also restores the graphene nano disk of different degree of oxidation and its electro-catalysis simultaneously
CO2The correlation for generating formic acid performance is also studied.
3, the preparation method of graphene nano disk provided by the invention, raw material is easy to get and process flow is simple, substantially reduces
Production cost, is conducive to large-scale industrialization application；And electrolyte is all common common salting liquid, does not add and appoints
What organic matter.
4, the graphene nano disk electro-catalysis CO of preparation method preparation provided by the invention2The formic acid generated is restored due to it
Energy density is high, is convenient for long-distance transport；Therefore it can be directly made into a kind of up-and-coming aminic acid fuel battery, is a kind of fine
Recycling CO2Method.
Detailed description of the invention
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the transmission electron microscope figure of graphene nano disk prepared by the embodiment of the present invention 1.
Fig. 2 is the atomic force microscopy diagram of graphene nano disk prepared by the embodiment of the present invention 1.
Fig. 3 is the atomic force microscopy diagram of different-thickness graphene oxide prepared by the present invention.
Fig. 4 is the electron paramagnetic resonance figure of graphene nano disk prepared by the embodiment of the present invention 1.
Fig. 5 is that graphene nano disk prepared by the embodiment of the present invention 1 restores CO2Linear sweep voltammetry figure.
Fig. 6 be the embodiment of the present invention 1 prepare graphene nano disk under different potentials by CO2It is restored to the farad of formic acid
Efficiency chart.
Fig. 7 is that the graphene nano disk that the embodiment of the present invention 1,2 and 3 is prepared under different hydrothermal temperatures restores CO2
Linear sweep voltammetry compare figure.
Fig. 8 is the graphene nano disk for preparing under different hydrothermal temperatures of the embodiment of the present invention 1,2 and 3 by CO2Also
Compare figure as far as the faradic efficiency of formic acid.
Fig. 9 is that graphene nano disk prepared by the embodiment of the present invention 1 is catalyzed CO at -0.68V2Reduction generates the core of formic acid
Magnetic testi figure.
Figure 10 is transmission electron microscope figure of the graphene nano disk of the preparation of embodiment 1 under another amplification factor.
Specific embodiment
The present invention provides a kind of preparation method for the graphene nano disk that size is controllable, pattern is uniform, comprising the following steps:
Using graphene oxide powder as raw material, using concentrated nitric acid as solvent, it is made that size is controllable, pattern is uniform by hydro-thermal method
Graphene nano disk.
It is preferred that the present invention is using the graphene oxide powder prepared by improved Hummers method as raw material (graphene
Thickness either single layer is also possible to multilayer)；The specific steps of which are as follows:
Natural graphite 1g is weighed, 0.74g NaNO is added3With 34mL 98%H2SO4, mix in ice-water bath, acutely stir
It mixes；It is slowly added to 5g KMnO later4, keep temperature to be lower than 20 DEG C, be then transferred to 35 DEG C of stirred in water bath 3 hours；Stirring
After be added 250mL deionized water, be slowly added to 4mL 30%wt H2O2Reaction was completed；Obtained glassy yellow suspension is first
With 5% hydrochloric acid solution centrifuge washing, to remove remaining H2SO4, then repeatedly cleaned with deionized water until pH is in neutrality；It will
Graphene solution after having washed is dried to obtain solid powder by freeze-drying or vacuum drying mode.
The graphene oxide powder prepared using above-mentioned improved Hummers method, using concentrated nitric acid as solvent, passes through as raw material
The obtained size of hydro-thermal method is uniform, thickness is only 1nm rich in oxygen defect graphene nano disk；And by this graphene nano disk material
Material restores CO for electro-catalysis2Generate formic acid.
It is preferred that the mass fraction of the concentrated nitric acid is 65%.
It is preferred that the preparation method specific steps for the graphene nano disk that the size is controllable, pattern is uniform include:
Dried graphene oxide powder is weighed, the concentrated nitric acid that mass fraction is 65% is added, the concentrated nitric acid adds
Enter volume is graphene oxide powder quality 1/10~1/20, ultrasonic agitation is until form evenly dispersed solution, Zhi Houfang
It sets in hydrothermal reaction kettle, is reacted 4~10 hours at 100-200 DEG C, after reaction kettle is cooled to room temperature, steamed using rotation
Hair, centrifugation and the mode dialysed repeatedly are added distillation water washing, collect, and drying obtains the graphite that size is controllable, pattern is uniform
Alkene nanometer plate.
It is preferred that the dosage of the graphene oxide powder is 400mg, the dosage of concentrated nitric acid is 20-40mL.
Further preferred reaction temperature is 140-180 DEG C.Most preferably reaction temperature is 160 DEG C, and the time is 6 hours.
The present invention also provides a kind of graphene nano disks of above-mentioned preparation method preparation.The size of the graphene nano disk
For 30nm~180nm, with a thickness of 1nm；And oxidizability g value reaches 2.01.
The present invention also provides a kind of graphene nano disks of above-mentioned preparation method preparation to restore dioxy for efficient electro-catalysis
Change the application that carbon generates formic acid.
The present invention is described in detail with reference to the accompanying drawing.
The preparation of graphene oxide raw material:
Natural graphite 1g is weighed, 0.74g NaNO is added3With 34mL 98%H2SO4, mix in ice-water bath, acutely stir
It mixes；It is slowly added to 5g KMnO later4, keep temperature to be lower than 20 DEG C, be then transferred to 35 DEG C of stirred in water bath 3 hours.Stirring
After be added 250mL deionized water, be slowly added to 4mL 30%wt H2O2Reaction was completed.Obtained glassy yellow suspension is first
With 5% hydrochloric acid solution centrifuge washing, to remove remaining H2SO4, then repeatedly cleaned with deionized water until pH is in neutrality.It will
Graphene solution after having washed is dried to obtain solid by freeze-drying or vacuum drying mode.
Embodiment 1: partial size is the preparation of the graphene nano disk of 70nm
The dried graphene oxide powder of 400mg is weighed, the concentrated nitric acid that the mass fraction of 40mL is 65%, ultrasound is added
The stirring 3 hours solution evenly dispersed up to formation, is placed in hydrothermal reaction kettle later, reacts 6 hours at 160 DEG C, to
After reaction kettle is cooled to room temperature, by the way of rotary evaporation, centrifugation and dialysis, 4~5 distillation water washings is added, collect,
Dry, obtaining partial size is 70nm, with a thickness of the graphene nano disk of 1nm.
Embodiment 2: partial size is the preparation of the graphene nano disk of 180nm
The dried graphene oxide powder of 400mg is weighed, the concentrated nitric acid that the mass fraction of 40mL is 65%, ultrasound is added
The stirring 3 hours solution evenly dispersed up to formation, is placed in hydrothermal reaction kettle later, reacts 4 hours at 140 DEG C, to
After reaction kettle is cooled to room temperature, by the way of rotary evaporation, centrifugation and dialysis, 4~5 distillation water washings is added, collect,
Dry, obtaining partial size is 180nm, with a thickness of the graphene nano disk of 1nm.
Embodiment 3: partial size is the preparation of the graphene nano disk of 30nm
The dried graphene oxide powder of 400mg is weighed, the concentrated nitric acid that the mass fraction of 40mL is 65%, ultrasound is added
The stirring 3 hours solution evenly dispersed up to formation, is placed in hydrothermal reaction kettle later, reacts 10 hours at 180 DEG C, to
After reaction kettle is cooled to room temperature, by the way of rotary evaporation, centrifugation and dialysis, 4~5 distillation water washings is added, collect,
Dry, obtaining partial size is 30nm, with a thickness of the graphene nano disk of 1nm.
Embodiment 4: partial size is the preparation of the graphene nano disk of 140nm
The dried graphene oxide powder of 400mg is weighed, the concentrated nitric acid that the mass fraction for being added 40 milliliters is 65% surpasses
Sound stirs the 3 hours solution evenly dispersed up to formation, is placed in hydrothermal reaction kettle, reacts 10 hours later at 100 DEG C,
After reaction kettle is cooled to room temperature, by the way of rotary evaporation, centrifugation and dialysis, 4~5 distillation water washings is added, receive
Collection, dry, obtaining partial size is 140nm, with a thickness of the graphene nano disk of 1nm.
Embodiment 5: partial size is the preparation of the graphene nano disk of 60nm
The dried graphene oxide powder of 400mg is weighed, the concentrated nitric acid that the mass fraction for being added 20 milliliters is 65% surpasses
Sound stirs the 3 hours solution evenly dispersed up to formation, is placed in hydrothermal reaction kettle, reacts 8 hours later at 200 DEG C,
After reaction kettle is cooled to room temperature, by the way of rotary evaporation, centrifugation and dialysis, 4~5 distillation water washings is added, receive
Collection, dry, obtaining partial size is more 60nm, with a thickness of the graphene nano disk of 1nm.
Embodiment 6
Graphene nano disk material generates the specific steps of the method for formic acid for efficient electro-catalysis reduction carbon dioxide:
In the three-electrode cell being separated by proton exchange membrane, graphene prepared by embodiment 1,2 and 3 is received respectively
Rice disk powder is mixed with ethyl alcohol, Nafion solution, ultrasonic disperse, is evenly coated on carbon paper, as working electrode, and platinized platinum is to electricity
Pole, saturated calomel electrode are reference electrode, electrolyte solution are respectively charged into cathode can and anode slot, and be passed through CO2It is extremely full
Be then continuously passed through CO2Under conditions of constant potential restore CO2, control of Electric potentials range in the constant potential reduction process
For -0.33V~-0.93V vs.RHE, the electroreduction time is 3~5h.Above-mentioned electrolyte solution is NaHCO3、KHCO3Or
Na2SO4Solution.
Fig. 1 is the transmission electron microscope figure of graphene nano disk prepared by the embodiment of the present invention 1；The figure can be seen that this
Circular ultra-thin lamellar structure is presented in graphene nano disk prepared by embodiment 1, and size is uniform.
Fig. 2 is the atomic force microscopy diagram of graphene nano disk prepared by the embodiment of the present invention 1；As can be seen from the figure its
Average thickness is 1nm.
Fig. 3 is the oxygen made from the preparation method of graphene oxide raw material according to the invention with a thickness of 0.7nm and 2nm
The atomic force microscopy diagram of graphite alkene；As can be seen from the figure two kinds of graphene oxide raw materials are in unformed lamella knot
Structure, and there are significant differences for thickness.This also illustrates that the preparation method of graphene nano disk provided by the invention is finally prepared
Nanometer plate shape it is unrelated with the thickness of raw material, using the graphene oxide raw material of different-thickness, it is controllable size can be obtained
, the graphene nano disk that pattern is uniform.
Fig. 4 is the electron paramagnetic resonance figure of graphene nano disk prepared by the embodiment of the present invention 1；The figure can be seen that utilization
The graphene nano disk degree of oxidation of this method preparation is very high, oxygen defect is abundant, and oxidation g value has reached 2.01.
Fig. 5 is that graphene nano disk prepared by the embodiment of the present invention 1 restores CO2Linear sweep voltammetry figure；It can from the figure
To find out the graphene nano disk material of the preparation to CO2Response it is very big.
Fig. 6 be the embodiment of the present invention 1 prepare graphene nano disk under different potentials by CO2It is restored to the farad of formic acid
Efficiency chart；As can be seen from the figure when current potential is in -0.68V, the faradic efficiency for generating formic acid reaches up to 87%；And
When starting overpotential only has 0.23V, the faradic efficiency for generating formic acid can still reach 28%.
Fig. 7 is that the graphene nano disk that the embodiment of the present invention 1,2 and 3 is prepared under different hydrothermal temperatures restores CO2
Linear sweep voltammetry compare figure；The figure illustrates the graphene nano disk synthesized under different hydrothermal temperatures to CO2's
Response is different, and temperature is that the electric current that the graphene nano dish cart at 160 DEG C reveals is maximum, and take-off potential is minimum.
Fig. 8 is the graphene nano disk for preparing under different hydrothermal temperatures of the embodiment of the present invention 1,2 and 3 by CO2Also
Compare figure as far as the faradic efficiency of formic acid；It can be seen from the figure that temperature is the graphene nano disk CO synthesized at 160 DEG C2
Reducing property is best.The peak value overpotential that temperature is 160 DEG C is significantly lower than the graphene nano disk at 180 DEG C, generates formic acid
Faradic efficiency is also apparently higher than under other two different temperatures.This also further demonstrates CO2Catalytic reduction performance with should
The degree of oxidation of material is related.
Fig. 9 is that graphene nano disk prepared by the embodiment of the present invention 1 is catalyzed CO at -0.68V2Reduction generates the core of formic acid
Magnetic testi figure.The figure illustrates: the detection composed by nuclear-magnetism NMR (AV 500) hydrogen detects formic acid, such as map logo institute really
Show；And it is quantified using DMSO as internal standard.
Figure 10 is transmission electron microscope figure of the graphene nano disk of the preparation of embodiment 1 under another amplification factor.From
The figure can be seen that the average grain diameter of prepared graphene nano disk is 70nm.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of preparation method of graphene nano disk, which comprises the following steps:
Using graphene oxide powder as raw material, using concentrated nitric acid as solvent, graphene nano disk is made by hydro-thermal method.
2. preparation method according to claim 1, which is characterized in that the graphene oxide powder passes through following methods system
It is standby to obtain:
Natural graphite 1g is weighed, 0.74g NaNO is added3With 34mL 98%H2SO4, mix, stir in ice-water bath；Later plus
Enter 5g KMnO4, keep temperature to be lower than 20 DEG C, be then transferred to 35 DEG C of stirred in water bath 3 hours；It is added after stirring
250mL deionized water adds 4mL 30%wt H2O2Reaction was completed；Obtained glassy yellow suspension is first used to 5% hydrochloric acid
Solution centrifuge washing, to remove remaining H2SO4, then repeatedly cleaned with deionized water until pH is in neutrality；By the stone after having washed
Black alkene solution is dried to obtain solid powder by freeze-drying or vacuum drying mode.
3. preparation method according to claim 1, which is characterized in that the mass fraction of the concentrated nitric acid is 65%.
4. preparation method according to claim 1, which is characterized in that its specific steps includes:
Dry graphene oxide powder is weighed, the concentrated nitric acid that mass fraction is 65%, the addition volume of the concentrated nitric acid is added
It is the 1/10~1/20 of graphene oxide powder quality, ultrasonic agitation is placed on water up to forming evenly dispersed solution later
It in thermal response kettle, is reacted 4~10 hours at 100-200 DEG C, after reaction kettle is cooled to room temperature, using rotary evaporation, centrifugation
With the mode of dialysis, distillation water washing is repeatedly added, collects, it is dry, obtain graphene nano that size is controllable, that pattern is uniform
Disk.
5. the preparation method according to claim 4, which is characterized in that the dosage of the graphene oxide powder is 400mg,
The dosage of concentrated nitric acid is 20-40mL.
6. the preparation method according to claim 4, which is characterized in that reaction temperature is 140-180 DEG C.
7. the preparation method according to claim 4, which is characterized in that reaction temperature is 160 DEG C, and the time is 6 hours.
8. a kind of graphene nano disk of the preparation of preparation method described in claim 1-7 any one.
9. graphene nano disk according to claim 8, which is characterized in that the size of the graphene nano disk is 30nm
~180nm, with a thickness of 1nm；And oxidizability g value reaches 2.01.
10. a kind of graphene nano disk of the preparation of preparation method described in claim 1-7 any one is used for efficient electro-catalysis
Restore the application that carbon dioxide generates formic acid.
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