CN108117066A - A kind of nitrogen-doped graphene quantum dot electrochemical preparation method - Google Patents
A kind of nitrogen-doped graphene quantum dot electrochemical preparation method Download PDFInfo
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Abstract
The present invention provides a kind of nitrogen-doped graphene quantum dot electrochemical preparation method, the preparation method is using D.C. regulated power supply as working power, with graphite rod (purity 99.999%) for anode and cathode, in (NH4)2SO4In aqueous solution, by adjusting the amount or electrolysis time of addition ammonium hydroxide, the nitrogen-doped graphene quantum dot of size uniformity is quickly separated using the method etching of electrochemical oxidation.Prepared nitrogen-doped graphene quantum dot, can be respectively applied to fluoroscopic examination and the improvement of electrode material for super capacitor performance.This method is easy to operate, equipment requirement is low, it is repeatable it is strong, product is stable, acid with strong oxidizing property or strong reductant is not used, be easy to scale and produce in enormous quantities and application.
Description
Technical field
The present invention relates to a kind of nitrogen-doped graphene quantum dot electrochemical preparing methods, in particular to Applied Electrochemistry to remove
Graphene introduces the preparation method and applications of N doping during generating quantum dot, which can answer
Used in numerous areas, such as fluoroscopic examination and the electrode material as ultracapacitor.The invention belongs to nano material prepare and
Application field.
Background technology
Graphene is a kind of carbon atom with SP2The hexangle type that hybrid form is formed is in the two-dimensional material of honeycomb lattice, special
And perfect structure has contained abundant and peculiar physical phenomenon, and graphene is made to show many excellent mechanics, calorifics, optics
And electrology characteristic, have in fields such as sensor, flexible transparent conductive film, lithium ion battery and ultracapacitors and widely should
Use prospect.
However compared with the graphene of perfect lattice structure, graphene quantum dot has swarmed into people as the semiconductor of zero band gap
The visual field.First, size has brighter in the zero dimension graphene quantum dot of below 10nm compared to the graphene nanometer sheet of two dimension
Aobvious quantum confined effect and stronger edge effect.Secondly, compared to traditional quantum dot and organic dyestuff, graphene amount
Son point has some more tempting properties, such as hypotoxicity, strong water-soluble, the prominent photostability of height etc..
In recent years, doping type graphene quantum dot become a big research hotspot, the graphene-doped lattice of heteroatom, no
The defects of band gap can be only effectively introduced into, but also graphene can be increased and the reactivity of local, so as to induce many
Special physicochemical characteristics.Meanwhile doping realizes the variation of graphene quantum dot level structure, in different exciting lights
The lower transmitting light that can send more different colours of irradiation, possesses efficient multicolor luminous characteristic.At present, N doping type graphene quantum
The preparation of point and its research of mechanism are more, and synthetic method can substantially be divided into " from bottom to top " from principle and " from upper
Under " method.
" from bottom to top " method in nucleation and carbonisation or then carries out nitrogen and mixes mainly using organic molecule as presoma
It is miscellaneous, including solution chemical method and microwave-hydrothermal method.Chinese patent (105197917 A of CN) glucose and the microwave spoke of ammonium hydroxide
According to the hydro-thermal reaction method that reaction method, (104710983 A of CN) are coordinated with metal ion with ethanolamine, nitrogen-doped graphene is formed
The problems such as quantum dot, but such method is related to microwave reactor, the regulation and control of high temperature and pressure, operating process high to equipment requirement
It is complicated, it is impossible to prepared by large-scale production.
" from top to bottom " method, by physics or chemical method by graphene film " cutting " into smaller graphene quantum
Point simultaneously or subsequently adds in nitrogen source and carries out N doping, mainly includes hydro-thermal method and electrochemical process.Hydro-thermal method technique mainly includes
Three steps：Graphene film is prepared first as carbon source；Then acidifying and oxidation obtain concentration higher and ruler in an acidic solution
Very little smaller derivative graphene film；Obtained product deoxidation and is finally introduced into nitrogen source under hydrothermal conditions, you can obtain nitrogen
Doped graphene quantum dot.Chinese patent (103113887 A of CN) is milled into powder as carbon source using carbon fiber, is forged through high temperature
It is scattered in after burning in concentrated nitric acid, water is added in after then high temperature flows back for a long time and ammonium hydroxide carries out hydro-thermal process.Chinese patent (CN
104150473 A) using graphite oxide and glycine, after azepine graphene film is made in argon atmosphere high annealing in strong acid
Ultrasonic cut generates quantum dot into oxidation nitrogen-doped graphene nanometer sheet, then hydro-thermal reaction.Hydro-thermal reaction needs multiple steps more
Suddenly, and strong acid participates in, and reaction time is long, and the preparation reaction temperature of nitrogen-doped graphene piece is high, and production cost is high, limits reality
Application in production.And electrochemical process processing carbon material is a kind of simple and effective method for preparing N doping carbene quantum dot,
If Chinese patent (106757138 A of CN) takes anhydrous ethylenediamine to add in lithium perchlorate, lead to nitrogen, anode and cathode is done with graphite rod, lead to
Enter after quantum dot solution prepared by DC power supply is spin-dried for and re-dissolve in water, then extracted with dichloromethane.This method needs lazy
Property gas shield, quantum dot dissolving, extraction and etc. be required for carrying out in organic solution, which has limited large-scale productions.
Up to the present, the high-volume controllable preparation nitrogen-doped graphene quantum dot of mild condition is still one without effective
It solves the problems, such as.
The content of the invention
The purpose of the invention is to overcome above-mentioned existing preparation process there are the defects of, providing one kind, to be easy to scale big
Batch production and the nitrogen-doped graphene quantum dot electrochemical preparation method of application, the preparation method is using D.C. regulated power supply as work
Make power supply, with graphite rod (purity 99.999%) for anode and cathode, in (NH4)2SO4In aqueous solution, ammonium hydroxide is added by adjusting
Amount or electrolysis time, the nitrogen-doped graphene quantum of size uniformity is quickly separated using the method etching of electrochemical oxidation
Point.The present invention uses following technical scheme：
A kind of preparation method of nitrogen-doped graphene quantum dot, described method includes following steps：
A. with graphite rod (the preferably graphite rod of purity 99.999%) for anode and cathode, concentration for 0.05~
(the NH of 0.5mol/L4)2SO4In aqueous solution, electrolytic cell is pre-processed by 4~10V potentiostatic depositions, makes anode, cathode
The graphite linings expansion on surface；
B. ammonium hydroxide is added into the pretreated electrolytic cells of step A, makes the NH in ammonium hydroxide3With (NH in step A4)2SO4Water
(NH in solution4)2SO4Molar ratio be 1~14:1, operating voltage in step A is kept to be electrolysed 60~180min, is then filtered
Electrolyte in electrolytic cell obtains pale yellow filtrate, by the pale yellow filtrate agitating and heating, to remove excessive ammonia；
C. by the filtrate that step B is obtained molecular cut off be 3000~12000Da bag filter in dialyse at room temperature to
Neutrality removes extra salt ion, obtains graphene quantum dot dispersion, the graphene quantum dot dispersion is freezed dry
It is dry, obtain the nitrogen-doped graphene quantum dot.
In above-mentioned preparation method, step A and step B electrolysis used in working power be D.C. regulated power supply.
In step A, electrode operating voltage oxygen evolution potential (during electrolysis water, theoretically O2/H2The current potential of O is 1.23V,
But actually generally require and reach 1.36V or so) more than when, can be electrolysed hydrone, generate hydroxyl and oxygen radical, serve as electricity
Chemical " scissors " function for cutting graphite, generates oxygen-containing functional group (electrolysis cutting graphite alkene quantum dot mechanism is shown in Fig. 1).
In order to balance electrolysis time needed for graphite expansion and effect, this experiment is minimum to use 4V operating voltages, the pre- place
The reason time is 30~120min.Sulfate ion size is more than spacing between graphene layer, can effectively carry out intercalation and stripping.
In above-mentioned preparation method, ammonium hydroxide preferred concentration described in step B is 26%, the pure ammonia of analysis that density is about 0.90g/ml
Water.
Film is filtered in above-mentioned preparation method, described in step B using polytetrafluoroethylene (PTFE) miillpore filter, preferably aperture is 0.22 μ
M can effectively remove residue in solution.
In above-mentioned preparation method, the pale yellow filtrate agitating and heating is preferably stirred the pale yellow filtrate described in step B
It heats 40~80 DEG C (boiling point of ammonium hydroxide is about 36 DEG C)；It is more preferably heated under the conditions of 40~80 DEG C, when heat preservation 1~3 is small, to remove
Remove excess of ammonia water.
In above-mentioned preparation method, the dialysis described in step C uses dialysis of the molecular cut off for 3000~12000Da
Bag applies needs according to different, selects different molecular weight bag filters；When dialysis time is 48~72 small, until solution is
Neutrality can effectively remove ammonium and sulfate ion.
In above-mentioned preparation method, in step C, the freeze-drying method is：In -84 DEG C of temperature, the condition of vacuum degree 4Pa
It is lower freeze-drying 48 it is small when, obtain dry solid-state nitrogen-doped graphene quantum dot powder.
Further, the preparation method of the nitrogen-doped graphene quantum dot preferably carries out as follows：
A. it is anode and cathode by 99.999% graphite rod of purity, in (the NH that concentration is 0.05~0.5mol/L4)2SO4In aqueous solution, electrolytic cell was pre-processed in 30~120 minutes by 4~10V potentiostatic depositions, make anode, cathode surface
Graphite linings expansion；
B. ammonium hydroxide is added into the pretreated electrolytic cells of step A, makes the NH in ammonium hydroxide3With (NH in step A4)2SO4Water
(NH in solution4)2SO4Molar ratio be 1~14:1, ammonium hydroxide keeps step for mass content in 25~28% pure ammonium hydroxide of analysis
Operating voltage is electrolysed 60~180 minutes in rapid A, is then filtered electrolyte and is obtained pale yellow filtrate, by the pale yellow filtrate
When heat preservation 1~3 is small under the conditions of being heated with stirring to 40~80 DEG C, to remove excessive ammonia；
C. in the bag filter for being 3000~12000Da in molecular cut off by the pale yellow filtrate that step B is obtained at room temperature
It is when dialysis 48~72 is small until neutral, extra salt ion is removed, obtains graphene quantum dot dispersion, by the graphene amount
Son point dispersion liquid obtains the nitrogen-doped graphene amount when freeze-drying 48 is small under conditions of -84 DEG C of temperature, vacuum degree 4Pa
Sub- point.
Beneficial effects of the present invention are as follows：
The method that the electrochemistry of the present invention prepares nitrogen-doped graphene quantum dot, using DC power supply under weak basic condition
Electrolytic graphite rod obtains water-soluble nitrogen-doped graphene fluorescence quantum.By controlling ammonium hydroxide additive amount, it is glimmering that its can be regulated and controled
Light color respectively obtains stable indigo plant, green fluorescence quantum dot, and solving needs high annealing, strong acid treatment, lazy in existing method
Property the harsh conditions such as gas shield or organic solvent system, while equipment requirement is low, is easy to scale and produces in enormous quantities and application.
Prepared nitrogen-doped graphene quantum dot, can also be applied to electrochemical energy storage field, pass through the compound quantum dot
The electric conductivity of electrode material activity substance can be improved, while realizes synergistic effect to improve the property of electrode material for super capacitor
Energy.
Description of the drawings
Fig. 1 is the mechanism schematic diagram that the present invention prepares nitrogen-doped graphene quantum dot；
Fig. 2 is the high resolution transmission electron microscopy piece of graphene quantum dot prepared by embodiment 1；
Fig. 3 is the X-ray diffractogram of graphene quantum dot prepared by embodiment 1；
Fig. 4 is the Fourier transform infrared spectroscopy figure of graphene quantum dot prepared by embodiment 1；
Fig. 5 is fluorescence photo and spectrogram of the graphene quantum dot of the preparation of embodiment 2 under different ammonium hydroxide additive amounts；
Fig. 6 is the ultraviolet-visible absorption spectroscopy figure of graphene quantum dot prepared by embodiment 2；
Fig. 7 is the CV figures of electrode before and after graphene quantum dot prepared by the compound embodiment 3 of nickel hydroxide；
Fig. 8 is the GCD figures of electrode before and after graphene quantum dot prepared by the compound embodiment 3 of nickel hydroxide.
Specific embodiment
With reference to specific embodiment, to a kind of electrochemical preparation method of nitrogen-doped graphene quantum dot of the present invention this
One technical solution and its application further elucidate.Ammonium hydroxide is analysis pure ammonium hydroxide of the mass content 26% in following embodiment.
Embodiment 1：It is prepared by the electrochemistry of nitrogen-doped graphene quantum dot
It is 0.5mol/L (NH in the concentration of 50ml with graphite rod (purity 99.999%) for anode and cathode4)2SO4It is water-soluble
In liquid, pre-processed within 120 minutes by 4V potentiostatic depositions, expand the graphite linings of electrode surface.Then into solution by
Drop addition 10ml ammonium hydroxide, is electrolysed 180 minutes, electrolyte then is filtered collection by vacuum and obtains pale yellow filtrate.By filtrate
Extra ammonium hydroxide is removed when heating stirring 3 is small under the conditions of 40 DEG C.Then in the bag filter for being 3500Da in molecular cut off thoroughly
2 day time is analysed to neutrality, extra ammonium root and sulfate ion is removed, obtains graphene quantum dot aqueous solution.It is saturating by what is obtained
Liquid freezing is analysed, when the freeze-drying 48 at -84 DEG C of temperature, vacuum degree 4Pa is small afterwards, obtains nitrogen-doped graphene quantum solid point
State powder.
Attached drawing 2 is the high resolution transmission electron microscopy piece of graphene quantum dot prepared by embodiment 1, as shown ruler
It is very little in 2~7nm, the graphene quantum dot being evenly distributed.
The X-ray diffractogram for the graphene quantum dot that attached drawing 3 is prepared for embodiment 1.
The Fourier transform infrared spectroscopy figure for the graphene quantum dot that attached drawing 4 is prepared for embodiment 1.
Embodiment 2：The electrochemistry of graphene quantum dot prepares and its regulation and control of fluorescence property
With graphite rod (purity 99.999%) for anode and cathode, the concentration for being inserted into 50ml is 0.1mol/L (NH4)2SO4Water
It in solution, is pre-processed within 60 minutes by 8V potentiostatic depositions so that graphite linings expand.By adding 1 respectively into solution,
2nd, 3,4,5ml ammonium hydroxide, is electrolysed 90 minutes, dispersion liquid then is filtered collection by vacuum and obtains pale yellow filtrate.Filtrate is existed
Extra ammonium hydroxide is removed when heating stirring 2 is small under the conditions of 60 DEG C.Then dialyse in the bag filter for being 12000Da in molecular cut off
To neutrality, extra ammonium root and sulfate ion are removed, obtains graphene quantum dot dispersion within 72 hours.Then added using ammonium hydroxide
The graphene quantum dot dispersion that dosage is 1,2,3,4,5 part carries out fluorescence spectrum and ultraviolet-visible absorption spectroscopy test respectively.
Used test equipment is SHIMADZU RF-6000 and UV-2700.
In the case where wavelength is the ultraviolet radiation of 365nm, the dispersion liquid fluorescence peak of 1ml ammonium hydroxide additive amounts is distributed in 450nm, shows
Stronger blue-fluorescence is shown；As a comparison, the dispersion liquid fluorescence peak of 5ml ammonium hydroxide additive amount is distributed in 495nm, shows green
Fluorescence.It is tested by fluorescence spectrum, quantum dot fluorescence color can be changed by adjusting ammonium hydroxide content.
Electrochemical process processing makes graphene quantum dot surface introduce the oxygen-containing groups such as substantial amounts of hydroxyl, epoxy, carbonyl and carboxyl
Group, while under ammonium hydroxide effect, amide C-N keys and amine C-N keys are generated respectively, as ammonium hydroxide increases, the quantum dot of preparation has
More defects, π-pi-conjugated system of quantum dot is gradually destroyed, and the pi-conjugated systems of n- gradually increase, so as to cause fluorescence color
Change.
Attached drawing 5 is fluorescence photo and spectrogram of the graphene quantum dot of the preparation of embodiment 2 under different ammonium hydroxide additive amounts.
The ultraviolet-visible absorption spectroscopy figure for the graphene quantum dot that attached drawing 6 is prepared for embodiment 2.
Embodiment 3：The electrochemistry of graphene quantum dot prepares and its application in electrochemical energy storage
With graphite rod (purity 99.999%) for anode and cathode, the concentration for being inserted into 50ml is the (NH of 0.05mol/L4)2SO4It in aqueous solution, is pre-processed within 30 minutes by 10V potentiostatic depositions so that graphite linings expand.Then into solution dropwise
0.5ml ammonium hydroxide is added, is electrolysed 300 minutes, dispersion liquid is then filtered into collection by vacuum and obtains pale yellow filtrate.Filtrate is existed
Extra ammonium hydroxide is removed when heating stirring 1 is small under the conditions of 80 DEG C.Then dialyse in the bag filter for being 5000Da in molecular cut off
To neutrality, extra ammonium root and sulfate ion are removed, obtains graphene quantum dot dispersion within 48 hours.The dialyzate that will be obtained
Freezing, when the freeze-drying 48 at -84 DEG C of temperature, vacuum degree 4Pa is small afterwards, obtains nitrogen-doped graphene quantum dot solid-state powder
End.
Nickel hydroxide nano piece and graphene quantum dot composite material prepare and electrode assembling is as follows：Nickel hydroxide nano
Piece synthesizes：20ml n,N-Dimethylformamide+0.2M 2ml nickel acetate solutions when 80 DEG C of stirrings 1 are small, then add 20ml water, water
180 DEG C of 10h of heat.By nickel hydroxide nano piece powder infusion into the solution containing nitrogen-doped graphene quantum dot (N-GQDs),
After ultrasonic disperse, vacuum drying obtains N-GQDs/Ni (OH)2Composite material.
By the material 85mg before and after the nickel hydroxide composite quantum dot of preparation, respectively with conductive agent carbon black, Kynoar
Binding agent is according to mass ratio 85:10:5 mixing are ground uniformly after then adding the N-Methyl pyrrolidone of 2ml, then divide
1cm is not coated in it2Foam nickel electrode on, drying box drying after, connect CHI 760D electrochemical workstation working electrodes, mercury/oxygen
Change mercury as reference electrode, platinized platinum as to electrode, tested in 1mol/L KOH are as the three-electrode system of electrolyte this two
The electrochemical energy storage performance of a electrode material simultaneously compares and analyzes.
Cyclic voltammogram of the attached drawing 7 for the electrode material before and after nickel hydroxide composite quantum dot under 20mV/s scanning voltages
Comparison；Fig. 8 is charge and discharge electrograph comparison of the electrode material of nickel hydroxide composite quantum dot under 1A/g current densities.Being computed can
Know Ni (OH)2The specific capacity of@GCD composite electrodes reaches 1656F/g, than Ni (OH)2Electrode (851A/g) is higher by nearly twice,
Show that nitrogen-doped graphene quantum dot has positive effect for the capacitive property for improving electrode material.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nitrogen-doped graphene quantum dot, described method includes following steps：
A. using graphite rod as anode and cathode, in (the NH that concentration is 0.05~0.5mol/L4)2SO4In aqueous solution, by 4~
10V potentiostatic depositions pre-process electrolytic cell, make the graphite linings expansion of anode, cathode surface；
B. ammonium hydroxide is added into the pretreated electrolytic cells of step A, makes the NH in ammonium hydroxide3With (NH in step A4)2SO4In aqueous solution
(NH4)2SO4Molar ratio be 1~14:1, operating voltage in step A is kept to be electrolysed 60~180min, then filters electrolytic cell
In electrolyte obtain pale yellow filtrate, by the pale yellow filtrate agitating and heating, to remove excessive ammonia；
C. the filtrate that step B is obtained is dialysed at room temperature in molecular cut off is the bag filter of 3000~12000Da to neutrality,
Extra salt ion is removed, obtains graphene quantum dot dispersion, the graphene quantum dot dispersion is freeze-dried, is obtained
The nitrogen-doped graphene quantum dot.
2. preparation method as described in claim 1, it is characterised in that：Step A, working power used in step B electrolysis is equal
For D.C. regulated power supply.
3. preparation method as described in claim 1, it is characterised in that：The time pre-processed described in step A for 30~
120min。
4. preparation method as described in claim 1, it is characterised in that：Vacuum filtration is micro- using polytetrafluoroethylene (PTFE) described in step B
Hole filter membrane.
5. preparation method as described in claim 1, it is characterised in that：Heating described in step B refers to be heated to 40~80 DEG C.
6. preparation method as claimed in claim 5, it is characterised in that：Heating described in step B refers to be heated to 40~80 DEG C,
And when heat preservation 1~3 is small.
7. preparation method as described in claim 1, it is characterised in that：The dialysis time dialysed described in step C is 48~72
Hour.
8. preparation method as described in claim 1, it is characterised in that：Described in step C freeze-drying be in -84 DEG C of temperature,
When freeze-drying 48 is small under conditions of vacuum degree 4Pa.
9. the preparation method as described in one of claim 1~8, it is characterised in that：The purity of the graphite rod is
99.999%.
10. the preparation method as described in one of claim 1~8, it is characterised in that：Described method includes following steps：
A. it is anode and cathode by 99.999% graphite rod of purity, in (the NH that concentration is 0.05~0.5mol/L4)2SO4Water
In solution, electrolytic cell was pre-processed in 30~120 minutes by 4~10V potentiostatic depositions, make the stone of anode, cathode surface
Layer of ink expands；
B. ammonium hydroxide is added into the pretreated electrolytic cells of step A, makes the NH in ammonium hydroxide3With (NH in step A4)2SO4In aqueous solution
(NH4)2SO4Molar ratio be 1~14:1, the ammonium hydroxide is the pure ammonium hydroxide of analysis of concentration 26%, keeps the electricity that works in step A
Then piezoelectricity solution 60~180 minutes filters electrolyte and obtains pale yellow filtrate, the pale yellow filtrate is heated with stirring to 40
When heat preservation 1~3 is small under the conditions of~80 DEG C, to remove excessive ammonia；
C. the pale yellow filtrate that step B is obtained is dialysed at room temperature in molecular cut off is the bag filter of 3000~12000Da
48~72 it is small when until neutral, remove extra salt ion, obtain graphene quantum dot dispersion, by the graphene quantum dot
Dispersion liquid obtains the nitrogen-doped graphene quantum dot when freeze-drying 48 is small under conditions of -84 DEG C of temperature, vacuum degree 4Pa.
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| CN111269714B (en) * | 2018-12-04 | 2022-07-29 | 中国科学院理化技术研究所 | Multi-fluorescence nitrogen-doped graphene quantum dot and preparation method and application thereof |
| CN112103089A (en) * | 2020-08-17 | 2020-12-18 | 上海大学 | Nitrogen-doped graphene quantum dot/eupolyphaga powder-based porous carbon composite material electrode, application and preparation method thereof |
| CN112103089B (en) * | 2020-08-17 | 2022-07-12 | 上海大学 | Nitrogen-doped graphene quantum dot/eupolyphaga powder-based porous carbon composite material electrode, application and preparation method thereof |
| CN113292140A (en) * | 2021-06-28 | 2021-08-24 | 长春工业大学 | Preparation method and application of nitrogen-doped titanium dioxide particle-loaded graphene-nickel foam membrane electrode |
| CN113582169A (en) * | 2021-08-11 | 2021-11-02 | 中钢集团南京新材料研究院有限公司 | Preparation method and application of graphene quantum dot with adjustable oxygen content |
| CN114014301A (en) * | 2021-11-17 | 2022-02-08 | 北京师范大学 | Synthetic method of fluorescent carbon nano onion |
| CN114014301B (en) * | 2021-11-17 | 2023-03-03 | 北京师范大学 | Synthetic method of fluorescent carbon nano onion |
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