CN105862057B - A kind of p-doped graphene quantum dot and its electrochemical preparation method - Google Patents
A kind of p-doped graphene quantum dot and its electrochemical preparation method Download PDFInfo
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- CN105862057B CN105862057B CN201610237919.1A CN201610237919A CN105862057B CN 105862057 B CN105862057 B CN 105862057B CN 201610237919 A CN201610237919 A CN 201610237919A CN 105862057 B CN105862057 B CN 105862057B
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Abstract
A kind of p-doped graphene quantum dot of present invention offer and its electrochemical preparation method, the preparation method selects the phosphorous larger molecular organics that can be dissolved in water as electrolyte, pass through potentiostatic deposition, make phosphorus oxygen bond rupture, phosphorus atoms are detached from larger molecular organics and enter inside graphene quantum dot, form carbon phosphorus key and phosphorus oxygen key, complete doping, the p-doped graphene quantum dot of highly doped content is prepared, the quantum dot has good scavenging effect to hydroxyl radical free radical, and test it by ESR power spectrums has reached 78.49% to the clearance rate of hydroxyl radical free radical.Operating process of the present invention is easy, whole preparation process is convenient for planning as a whole, acid with strong oxidizing property or strong reductant is not used, with certain commercial viability.With this deposit of graphite, abundant, environmentally friendly presoma is expected to be widely applied in biomedical sector instead of expensive materials such as graphite oxide, carbon nanotubes.
Description
Technical field
The invention belongs to radicals scavenging fields, and in particular to a kind of p-doped graphene quantum dot and its electrochemistry preparation side
Method.
Background technology
Free radical is chemically also referred to as " free radical ", refer to compound molecule under the external conditions such as photo-thermal, covalent bond
The atom or group with unpaired electron that fracture occurs and is formed.In the reaction of human metabolism, suitable freedom
Base plays transmission energy, kills the effect of harmful bacteria, but when free radical excess, interfere with cell normal operation, accelerates thin
Born of the same parents' aging in turn results in various diseases.Today's society, with the development of industry, the pollution of environment, the kinds such as increasing of life stress
Kind reason, the chance that people contact free radical is increasing, and cosmetics such as inferior are harmful to food additives, tobacco, anxiety
Deng can all cause human free radical excessive, various diseases are in turn resulted in.In addition to human body, it has also been found that free radical can also cause to be permitted
The erosion of more organic materials and high molecular material, to influence service life and performance.Various harms of free radical are
The extensive concern of people is caused, is largely also unfolded therewith about the research for removing free radical.In carbon material field, fullerene is most
It is early found to have the ability for removing free radical, reason is the ability of the high attraction electronics caused by its molecular structure, but
Fullerene manufacturing cost is higher, and in order to make it have hydrophily and biocompatibility, still has a large amount of subsequent processing to walk
Suddenly it needs to complete, so limiting its large-scale application.Carbon nanotube also be used to have because it captures the ability of free radical
The LP blades of machine high molecular material remove the abilities such as free radical and are attributed to the defect inside molecular structure, but carbon nanotube water
Dissolubility and biocompatibility are poor, limit its application in biomedical aspect.Shaojing zhao etc. once prepare one
Kind has the nitrogen sulphur codope carbon quantum dot for removing DPPH free radicals（Zhao S, Lan M, Zhu X, et al. [J].
ACS applied materials & interfaces, 2015, 7(31): 17054-17060.）, but the carbon quantum dot is simultaneously
It does not show to the good Scavenging activity of hydroxyl radical free radical.And the member new as carbon material family, graphene quantum dot is clear
Research not yet someone in terms of except free radical reports, because graphene quantum dot has the energy for attracting electronics as fullerene
Power has certain defect and the molecular structure of carbon quantum dot especially similar as carbon nanotube.Again because of graphene quantum dot
With good water solubility, biocompatibility etc.（Have many cell characterizations studied and graphene quantum dot applied in human body
Among）, therefore we have proposed the trials that doping type graphene quantum dot is applied to removing free radical, and achieve preferable
Effect.
Doping has been widely studied as a kind of method of Effective Regulation material property, in graphene quantum dot field, is
More better performances of acquisition and widely application, many doping type graphene quantum dots are also synthesized.Study table
Bright foreign atom can enter inside graphene quantum dot molecular structure, influence its various internal performance, including element composition, charge
Density, energy gap, polarizability etc., and then change photoluminescence performance, constituent content, catalytic performance, size and surface topography
Equal macro properties.By people's extensive concern, a collection of nitrating mixes sulphur, mixes for the research being doped in recent years to graphene quantum dot
The graphene quantum dot of boron etc. and various codopes is studied successfully.Li Xueming etc. has been prepared using hydro-thermal method with multiple
Fluorescent emission peak value mix sulfur graphite alkene quantum dot (Li X, Lau S P, Tang L, et al. [J] Nanoscale,
2014, 6(10):5323-5328.), the fluorescence probe prepared using hydro-thermal method and can be used for detecting glucose such as vertical is opened
Boron-doped graphite alkene quantum dot (Zhang L, Zhang Z Y, Liang R P, et al. [J] Analytical
chemistry, 2014, 86(9):4423-4430.), Sunita Dey etc. are prepared for the boron with up-conversion luminescence property
Nitrogen co-doped graphene quantum dot (Dey S, Govindaraj A, Biswas K, et al. [J] Chemical
Physics Letters, 2014, 595: 203-208.).In conclusion the method by foreign atom is carried out to graphene
The regulation and control of the various performances of quantum dot are feasible, and the graphene quantum dot property that some did not had originally can also be assigned by doping
Energy.
These doping methods mostly use greatly hydro-thermal method progress, so-called hydro-thermal method, refer to using big size graphene piece as carbon source,
Graphene oxide sheet and small size graphene quantum dot is prepared in the environment of strong acid strong oxidizer via hydrothermal reduction.It is this
Method advantage is that yield is big, and design is simple, and disadvantage is in operating process largely to use dangerous strong acid strong oxidizer etc.,
And the graphene quantum spot size prepared is often also inhomogenous.During preparing doped graphene quantum dot, hydro-thermal
Method is to push the fracture of old chemical bond and the formation of new chemical bond by feat of the oxidation potential of strong oxidizer, and strong oxidizer
Potential is again often constant, can not be broken the stronger chemical bond of some bond energys, therefore this method is preparing the small member of doping difficulty
It can also successfully be prepared when the graphene quantum dot that element is adulterated, but then helpless for the larger element of some doping difficulty.
P elements are exactly the larger element of such a doping difficulty, and one side P elements usually exist with phosphorus oxygen key-shaped formula, phosphorus oxygen key
Bond energy is very strong, and conventional method is difficult to open, and another aspect phosphorus atoms and carbon atom size and the equal difference of electronegativity are very big, it is difficult to mix
Enter graphene quantum dot intramolecule, form stable structure, and once adulterate success, then it is completely new to assign graphene quantum dot
Performance, such as remove free radical ability.And the doping that electrochemical method is then P elements specifies new road, so-called electrification
Method refers to, using platinum electrode or silver/silver chloride electrode as reference electrode, choosing suitable electricity using high purity graphite bar electrode as carbon source
Liquid and electroaffinity are solved, the method for the high oxidative free radical generated by electrolysis water, oxidation cutting high purity graphite rod prepares stone
Black alkene quantum dot, and when preparing doped graphene quantum dot can selectivity give enough potentials, with promote doping member
The intercalation and bonding of element.The advantages of this method is operating process simplicity, whole preparation process convenient for pool, unused Strong oxdiative
Property acid or strong reductant, with certain commercial viability.Especially abundant, the environmentally friendly forerunner with this deposit of graphite
Body is instead of expensive materials such as graphite oxide, carbon nanotubes.Therefore this p-doped quantum dot is because of its good removing free radical energy
The preparation method of power and simple low cost, is expected to be widely applied in biomedical sector.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of electrochemical preparation method of p-doped graphene quantum dot, described
Preparation method selects the phosphorous larger molecular organics that can be dissolved in water as electrolyte, passes through potentiostatic deposition so that phosphorus oxygen key is disconnected
It splits, phosphorus atoms are detached from larger molecular organics and enter inside graphene quantum dot, form carbon phosphorus key and phosphorus oxygen key, complete doping, system
Obtain p-doped graphene quantum dot；
Further, noxious material is not generated during described larger molecular organics itself are nontoxic and electrolytic process；
Further, the method specifically includes：
Step 1）The electrolyte of the 0.1mol/L of 40mL is added in reaction vessel, and by a ultrapure graphite stick and a platinum
Plate electrode is inserted into electrolyte as working electrode and to electrode；
Step 2）By above-mentioned steps 1）In electrode be connected to electrochemical workstation, prepared using electrochemistry potentiostatic method
The sepia graphene quantum dot aqueous solution of p-doped is filtered and dialyses to the graphene quantum dot aqueous solution, obtains transparent
Amber graphene quantum dot aqueous solution；
Step 3）The p-doped graphene quantum dot aqueous solution that dialysis is finished carries out hydroxyl radical free radical removing using ESR power spectrums
The source of the detection of ability, hydroxyl radical free radical is ultraviolet lighting hydrogen peroxide, and needs to be added DMPO in solution to stablize hydroxyl
Free radical；
Further, the step 1）In electrolyte be sodium phytate solution；
Further, the step 2）In voltage be 3 ~ 5V, sweep time be 2h ~ 12h, to the amber graphite
Alkene quantum dot aqueous solution is filtered using the filtering head of 220nm, uses molecular cut off for the bag filter of 3500 ~ 14000Da
It dialyses；
Further, the step 3）The middle free radical that carries out understands that the sample of aptitude tests is p-doped graphene quantum dot；
A kind of p-doped graphene quantum dot, the p-doped graphene quantum dot have free radical scavenging ability.
Beneficial effects of the present invention are as follows：
1）Operating process is easy, whole preparation process is convenient for planning as a whole, acid with strong oxidizing property or strong reductant is not used, has one
Fixed commercial viability；
2）Especially with this deposit of graphite enriches, environmentally friendly presoma is instead of graphite oxide, carbon nanotubes
Etc. expensive materials；The preparation method of good Scavenging ability and simple low cost is expected to obtain in biomedical sector
It is widely applied；
3）P elements usually with phosphorus oxygen key-shaped formula exist, phosphorus oxygen key bond energy is very strong, conventional method be difficult open, phosphorus atoms with
Carbon atom size and the equal difference of electronegativity are very big, it is difficult to and graphene-doped quantum dot intramolecule forms stable structure, and one
Denier is adulterated successfully, then can assign the ability that graphene quantum dot removes free radical.
Description of the drawings
Fig. 1 is the molecular structure of sodium phytate used in the present invention；
Fig. 2 is quick preparation and the radicals scavenging experimental method flow chart of p-doped graphene quantum dot of the present invention.
Specific implementation mode
In order to make the purpose of the present invention, technology example and advantage be more clearly understood, with reference to the accompanying drawings and embodiments, to this
Invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, not
For limiting the present invention.On the contrary, the present invention cover it is any be defined by the claims done in the spirit and scope of the present invention
Replacement, modification, equivalent method and example.Further, in order to make the public have a better understanding the present invention, below to the present invention
Datail description in, it is detailed to describe some specific detail sections.Portion without these details for a person skilled in the art
The description divided can also understand the present invention completely.
The invention will be further described in the following with reference to the drawings and specific embodiments, but not as a limitation of the invention.
Below most preferred embodiment is enumerated for the present invention：
As Figure 1-Figure 2, a kind of p-doped graphene quantum dot of present invention offer and its electrochemical preparation method, utilize electricity
Chemical potentiostatic method chooses suitable electrolytes, electrolysis time prepares the graphene amount of highly doped phosphorus content by controlling voltage
It is sub-, and the quantum dot has the ability of excellent removing free radical, is a kind of idea and method of new removing free radical.
P-doped graphene quantum dot is prepared by constant potential electrochemical method, core is to choose suitable electrolyte, this
Kind electrolyte must be a kind of phosphorous, can be dissolved in the larger molecular organics of water, and in itself nontoxic and preparation process
Noxious material is not generated, therefore we have selected sodium phytate, this is a kind of green food additive, and molecular structure is shown in Fig. 1, is being planted
In sour sodium molecule, phosphorus atoms are connected by a bridge oxygen atom with a six-membered carbon ring, six-membered carbon ring macromolecular and and phosphorus
The presence of connected macromolecular structure makes phosphorus oxygen key more easy fracture, so that phosphorus atoms, which can be detached from sodium phytate, enters graphite
Inside alkene quantum dot, new chemical bond is formed（Carbon phosphorus key and phosphorus oxygen key）, complete doping process.Can the selection of electrolyte is at
Can work(adulterates the key of P elements, and with the key of high Scavenging ability, we are using equally containing phosphorus member
Element inorganic electrolyte liquid --- phosphate buffer solution is electrolysed with same potential, and graphite has also been prepared after a period of time
Alkene quantum dot, but XPS and infrared results show the quantum dot and undoped with P elements, also do not show high free radical and understand
Ability.
Process such as Fig. 2 of p-doped graphene quantum dot is prepared, compound concentration first is the sodium phytate solution of 0.1mol/L, it
Electrochemistry potentiostatic method is used to prepare p-doped graphene quantum dot aqueous solution afterwards.The electrochemical cyclic voltammetry uses ultrapure stone
Inker and platinum plate electrode are working electrode and to electrode, and the working electrode, to be placed in the electrolyte in reaction unit to electrode molten
In liquid, electrochemical parameter setting：Constant voltage is 3 ~ 5V, and sweep time is 2h ~ 12h.It is prepared using electrochemical cyclic voltammetry
In the process, brown liquid is generated first, and the brown liquid is the graphene quantum dot aqueous solution with impurity, to described
Brown liquid is dialysed, and uses molecular cut off to dialyse for the bag filter of 3500 ~ 14000Da, dialysis time is 5 ~ 9
It finally obtains transparent light brown aqueous solution per changing a deionized water at regular intervals, described transparent amber
Aqueous solution is p-doped graphene quantum dot aqueous solution.The concentration of solution is measured, and carries out x-ray photoelectron spectroscopy and infrared spectrum
Test determines the content of P elements and the type and content of typical oxygen-containing functional group.In order to prove the key of electrolyte, I
Be provided with the same phosphorous phosphate buffer solutions of same concentrations as electrolyte, control is all in addition to electrolyte
Parameter is identical as sodium phytate electrolyte, finally also carries out x-ray photoelectron spectroscopy and infrared spectrum to the quantum dot prepared
Test, it is determined whether can also adulterate P elements, as a result show that P elements do not adulterate success.It is carried out finally by ESR power spectrums
The removing of hydroxyl radical free radical is tested, and hydroxyl radical free radical source is ultraviolet lighting hydrogen peroxide.
Embodiment 1：
Compound concentration is the sodium phytate solution (NaP) of 0.1mol/L, and a high purity graphite rod and a platinum plate electrode are inserted
Enter solution as working electrode and to electrode.Constant potential is set as 5V, and sweep time is set as 12h.The solution is obtained
Brown aqueous solution is filtered with the filtering head of 220nm, is then carried out with the bag filter that molecular cut off is 3500 ~ 14000Da
Dialysis, removes extra ion, obtained light brown solution is calculated as sample 1.The phosphate-buffered of configuration same concentrations is molten later
Liquid (PBS), control is identical with above-mentioned condition parameter, only changes electrolyte, the quantum dot that this method is prepared is calculated as
Sample 2.
The GQDs aqueous solutions of above-mentioned preparation, the clean silicon chip surface of drop coating to 0.5 × 0.5 cm, by infrared light are taken respectively
Spectrum and x-ray photoelectron spectroscopy test show：Two kinds of electrolyte have all prepared graphene quantum dot solution, but only sample 1,
Namely sodium phytate electrolyte (NaP) prepare it is quantum dot-doped gone up P elements, and sample 2, that is, phosphate-buffered
The quantum dot that solution is prepared is undoped with upper P elements, and the oxygen content of two amounts sub- point, and various functional group contents are also
It is different.The removing test of hydroxyl radical free radical is carried out by ESR power spectrums, hydroxyl radical free radical source is ultraviolet lighting hydrogen peroxide, certainly
It is removed in test experiments by base, the graphene quantum dot of p-doped has reached 78.49% to the clearance rate of hydroxyl radical free radical, this explanation
The p-doped graphene quantum dot has the good ability for removing free radical, and the graphene quantum dot undoped with upper P elements is simultaneously
High free radical scavenging ability is not shown.
Embodiment 2：
Compound concentration is the sodium phytate of 0.1mol/L（NaP）Solution inserts a high purity graphite rod and a platinum plate electrode
Enter as working electrode and to electrode, is scanned using electrochemistry potentiostatic method.Scanning voltage is set as 3V, and sweep time is
Then obtained brown aqueous solution is filtered by 12h with the filtering head of 220nm, then use molecular cut off be 3500 ~
The bag filter of 14000Da is dialysed, and extra ion is removed.
Take the GQDs aqueous solutions of above-mentioned preparation, the clean silicon chip surface of drop coating to 0.5 × 0.5 cm, by infrared spectrum and
X-ray photoelectron spectroscopy tests whether successfully to have adulterated P elements, then the survey of radicals scavenging experiment is carried out by ESR power spectrums
Whether examination, seeing has high free radical scavenging ability.
Embodiment 3：
Compound concentration is the sodium phytate of 0.1mol/L（NaP）Solution inserts a high purity graphite rod and a platinum plate electrode
Enter as working electrode and to electrode, is scanned using electrochemistry potentiostatic method.Scanning voltage is set as 5V, and sweep time is
Then obtained brown aqueous solution is filtered by 2h with the filtering head of 220nm, then use molecular cut off be 3500 ~
The bag filter of 14000Da is dialysed, and extra ion is removed.
Take the GQDs aqueous solutions of above-mentioned preparation, the clean silicon chip surface of drop coating to 0.5 × 0.5 cm, by infrared spectrum and
X-ray photoelectron spectroscopy tests whether successfully to have adulterated P elements, then the survey of radicals scavenging experiment is carried out by ESR power spectrums
Whether try has high free radical scavenging ability.
Embodiment described above, only one kind of the present invention more preferably specific implementation mode, those skilled in the art
The usual variations and alternatives that member carries out within the scope of the technology of the present invention example should be all included within the scope of the present invention.
Claims (6)
1. a kind of electrochemical preparation method of p-doped graphene quantum dot, which is characterized in that the preparation method selects phosphorous energy
The larger molecular organics of water are dissolved in as electrolyte, pass through potentiostatic deposition so that phosphorus oxygen bond rupture, phosphorus atoms are detached from macromolecular
Organic matter enters inside graphene quantum dot, forms carbon phosphorus key and phosphorus oxygen key, completes doping, and p-doped graphene quantum dot is made,
The larger molecular organics include six-membered carbon ring macromolecular and are connected with phosphorus, and described larger molecular organics itself are nontoxic and are electrolysed
Noxious material is not generated in journey, the larger molecular organics are sodium phytate.
2. preparation method according to claim 1, which is characterized in that the method specifically includes：
The electrolyte of the 0.1mol/L of 40mL is added in step 1) reaction vessel, and by a ultrapure graphite stick and a platinized platinum electricity
Pole is inserted into electrolyte as working electrode and to electrode；
Step 2) is by above-mentioned steps 1) in electrode be connected to electrochemical workstation, p-doped is prepared using electrochemistry potentiostatic method
Sepia graphene quantum dot aqueous solution, which is filtered and is dialysed, is obtained transparent light
The graphene quantum dot aqueous solution of brown；
The p-doped graphene quantum dot aqueous solution that step 3) finishes dialysis carries out hydroxyl radical free radical Scavenging activity using ESR power spectrums
Detection, the source of hydroxyl radical free radical is ultraviolet lighting hydrogen peroxide, and needs to be added DMPO in solution to stablize hydroxyl free
Base.
3. preparation method according to claim 2, which is characterized in that the electrolyte in the step 1) is that sodium phytate is molten
Liquid.
4. preparation method according to claim 2, which is characterized in that voltage in the step 2) is 3~5V, when scanning
Between be 2h~12h, the amber graphene quantum dot aqueous solution is filtered using the filtering head of 220nm, using cutting
It is that the bag filter of 3500~14000Da is dialysed to stay molecular weight.
5. preparation method according to claim 2, which is characterized in that carry out free radical scavenging ability survey in the step 3)
The sample of examination is p-doped graphene quantum dot.
6. a kind of p-doped graphene quantum dot, based on the preparation method described in one of the claims 1-5, which is characterized in that
The p-doped graphene quantum dot has free radical scavenging ability.
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| CN109336087A (en) * | 2018-12-26 | 2019-02-15 | 南京林业大学 | Cork oak acorn-cup base carbon quantum dot and its application on fluorescent ink are prepared using cork oak acorn-cup |
| CN110203922B (en) * | 2019-06-26 | 2020-10-20 | 武汉中科先进技术研究院有限公司 | Preparation method of functionalized carbon material |
| EP4155265A1 (en) | 2020-05-21 | 2023-03-29 | Kureha Corporation | Composition and method for producing same |
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