CN103382029A - Graphite with surface modified by azido groups and preparation method thereof - Google Patents
Graphite with surface modified by azido groups and preparation method thereof Download PDFInfo
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- CN103382029A CN103382029A CN201310253060XA CN201310253060A CN103382029A CN 103382029 A CN103382029 A CN 103382029A CN 201310253060X A CN201310253060X A CN 201310253060XA CN 201310253060 A CN201310253060 A CN 201310253060A CN 103382029 A CN103382029 A CN 103382029A
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Abstract
The invention discloses graphite with the surface modified by azido groups and a preparation method thereof. The method comprises the steps: in an electrolyte solution with the azide ion concentration of 1 mol/L to 2 mol/L, employing a three-electrode system, with a graphite sheet as an anode, a platinum sheet electrode as a cathode and a saturated calomel electrode as a reference electrode, and applying a constant electric potential of 0.5-2 V or a constant current of 10-60 mA to treat the graphite sheet electrode for 10-60 min; soaking the treated graphite sheet electrode in methanol, and then drying at the room temperature to obtain the graphite sheet with the surface modified by the azido groups. The method of the invention has high selectivity, does not introduce other groups or atoms to the surface of graphite, allows the reaction to be carried out without cooling conditions, has low-price raw materials, does not employ organic solvents, and only needs one step reaction.
Description
Technical field
The invention belongs to the materials chemistry field, relate to a kind of graphite of modifying the method for azido-and utilizing the finishing azido-of the method preparation at graphite surface by electrochemical method.
Background technology
Graphite-phase is widely used in the research directions such as electroanalysis, electrolytic preparation than other electrode materials low price, easy to process always, and it is as the most cheap carbon electrode material, and the graphite of functionalization is the study hotspot of Material Field always.In order to expand its range of application, the functional molecular that will have a good electrochemical properties is modified graphite surface to be become in recent years by the focus of extensive concern.Such as (J.Am.Chem.Soc. such as Anando Devadoss, 2007,129,5370-5371) a kind of method of azido-directly being modified graphite surface is disclosed, and utilize azido-and carry out cycloaddition reaction with the alkynes of active group, the ferrocene group that should have electrochemical activity is modified graphite electrode surface, has certain application prospect aspect sensor.Elizabeth C.Landis(Chem.Mater, 2009,21,724-730) also use the same method on the electrode that carbon nanofiber is modified by obtaining the electrochemical activity functional molecular with its azido-that directly is connected.In addition: James P.Collman, wait the people (.Langmuir2006,22,2457-2464) also modify terminal on platinum electrode and reach the purpose of other functional group of link with the molecule of azido group.
(the J.Am.Chem.Soc. such as contrast Anando Devadoss, 2007,129,5370-5371) with Elizabeth C.Landis(Chem.Mater, 2009,21, modifying method 724-730), be all by reacting at low temperatures the generation iodazide at iodine monochloride and sodiumazide at the anhydrous acetonitrile solvent, then reaction solution obtains the finished product with the graphite flake effect again.
The aforesaid method weak point is: make a certain amount of iodine also be modified at graphite surface with the form of covalent linkage when azido-in (1) connection, selectivity is relatively poor; (2) iodine monochloride reagent is expensive; (3) need to an organic solvent prepare intermediate azide iodine under cooling conditions; (4) need two-step reaction.
Summary of the invention
The present invention seeks to provide a kind of method that solely azido-is connected to graphite surface, and the surface that utilizes the method to prepare to be connected with the graphite of azido-for existing method deficiency.
In order to realize above-mentioned task, the scheme that the present invention adopts is:
A kind of preparation method of graphite of finishing azido-, the method comprises the following steps:
Step 1 is in the electrolyte solution of 1～2mol/L in nitrine radical ion concentration, uses three-electrode system, with graphite flake as anode,, as reference electrode, the graphite flake electrode is applied 10～60mA continuous current process 10～60min with saturated calomel electrode as negative electrode with platinum plate electrode;
Step 2, the graphite flake electrode after step 1 is processed soaks rear dry in methyl alcohol, obtains the graphite of finishing azido-.
A kind of graphite that utilizes the finishing azido-of aforesaid method preparation.
Further, the electrolyte solution described in step 1 is the sodiumazide aqueous solution, the Lithium Azide aqueous solution or the potassium azide aqueous solution.
Replaceable 0.5～the 2V of being of the 10～60mA continuous current constant potential that in step 1, the graphite flake electrode is applied.
Electrolyte solution described in step 1 preferably adopts the sodium azide solution of 1mol/L, and the continuous current that the graphite flake electrode applies is 20mA, and the treatment time is 30min
The present invention's advantage compared with prior art:
In the present invention, the method for graphite surface modification azido-has highly selective, does not introduce other group or atom to graphite surface, and reaction need not cooling conditions, and cost of material is cheap, not with an organic solvent, and only needs single step reaction; Compare with existing method, the inventive method has the advantages such as cost is low, the preparation method is easy, has broad application prospects at electron device, electrode materials, sensor area research.
Description of drawings
Fig. 1 is the X-photoelectron spectrum figure that the table of embodiment 1 preparation is modified the graphite flake of azido-;
Fig. 2 is the X-photoelectron spectrum figure N1s high resolution X-photoelectron spectrum figure of graphite flake of the finishing azido-of embodiment 1 preparation;
Fig. 3 is the attenuated total reflectance attenuated total refraction infrared spectrogram of graphite flake of the finishing azido-of embodiment 1 preparation.
Embodiment
The present invention is achieved by the following technical solutions: in the aqueous solution that contains nitrine root (N3-), take graphite flake as anode, apply certain voltage or electric current, utilize nitrine root and graphite surface generation electrochemical reaction that azido-is modified on graphite, specifically comprise the following steps:
Step 1 is in the electrolyte solution of 1～2mol/L in nitrine radical ion concentration, uses three-electrode system, with graphite flake as anode,, as reference electrode, the graphite flake electrode is applied 10～60mA continuous current process 10～60min with saturated calomel electrode as negative electrode with platinum plate electrode;
Step 2, the graphite flake electrode after step 1 is processed soaks rear dry in methyl alcohol, obtains the graphite of finishing azido-.
Electrolyte solution described in step 1 is the sodiumazide aqueous solution, the Lithium Azide aqueous solution or the potassium azide aqueous solution; Replaceable 0.5～the 2V of being of the 10～60mA continuous current constant potential that in step 1, the graphite flake electrode is applied.In described three-electrode system, but negative electrode also copper plate electrode or nickel plate electrode; In following embodiment, it is the graphite flake of 2.0*2.0*0.3cm that the graphite flake electrode that adopts all adopts specification, and namely length and width is 2cm, thickness is the graphite flake of 0.3cm, perhaps selects the graphite flake less than this size of 2.0*2.0*0.3cm.
Below in conjunction with drawings and Examples, the present invention is elaborated, need to prove, this embodiment is more excellent example, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
A kind of preparation method of graphite of finishing azido-, the method comprises the following steps:
Step 1 in the sodium azide solution of 1mol/L, is used three-electrode system, with graphite flake as anode,, as reference electrode, with electrochemical workstation, the graphite flake electrode is applied the 20mA continuous current and process 30min with saturated calomel electrode as negative electrode with platinum plate electrode;
Step 2, (25 ℃) drying at room temperature after the graphite flake electrode after step 1 is processed soaks in methyl alcohol obtains the graphite of finishing azido-.
Fig. 1 and Fig. 2 are respectively the X-photoelectron spectrum full figure scanning of graphite flake of finishing azido-of embodiment 1 method preparation and the fine scanning of N1s; As can be seen from the figure azido group center nitrogen-atoms signal 404eV left and right and other two atoms are at the signal of 400ev left and right, and its peak area ratio is 1:2; , without other impurity element signals such as metals.
Fig. 3 is the infrared spectra attenuated total reflectance attenuated total refraction figure that the finishing of embodiment 1 preparation has the graphite flake of azido-, as can be seen from the figure the infrared absorption 2100cm of azido-
-1The absorption peak of effect, c h bond 2900cm
-1, 2850cm
-1, 2350cm
-1Two of left and right absorption peak is the CO of absorption
2Signal.
By above sign, can see that azido-successfully modifies on carbon nanotube, and not introduce other elements, it is 2.1% that x-ray photoelectron spectroscopy (XPS) characterizes the surperficial relative content that draws the N element.
Embodiment 2
The preparation method of this embodiment is as follows:
Step 1 in the potassium azide solution of 2mol/L, is used three-electrode system, with graphite flake as anode,, as reference electrode, with electrochemical workstation, the graphite flake electrode is applied the 0.6V constant potential and process 60min with saturated calomel electrode as negative electrode with platinum plate electrode;
Step 2, the graphite flake electrode after step 1 is processed soaks under rear room temperature dry in methyl alcohol, obtains the graphite of finishing azido-.
The graphite flake of the finishing azido-of the present embodiment preparation, it is 1.2% that XPS characterizes the surface-element relative content that draws the N element.
Embodiment 3
The preparation method of this embodiment is as follows:
Step 1 in the Lithium Azide solution of 1.5mol/L, is used three-electrode system, with graphite flake as anode,, as reference electrode, with electrochemical workstation, the graphite flake electrode is applied the 10mA continuous current and process 60min with saturated calomel electrode as negative electrode with platinum plate electrode;
Step 2, the graphite flake electrode after step 1 is processed soaks under rear room temperature dry in methyl alcohol, obtains the graphite of finishing azido-.
The graphite flake of the finishing azido-of the present embodiment preparation, it is 1.5% that XPS characterizes the surface-element relative content that draws the N element.
Embodiment 4
The preparation method of this embodiment is as follows:
Step 1 in the sodium azide solution of 1mol/L, is used three-electrode system, with graphite flake as anode,, as reference electrode, with electrochemical workstation, the graphite flake electrode is applied the 60mA continuous current and process 10min with saturated calomel electrode as negative electrode with platinum plate electrode;
Step 2, the graphite flake electrode after step 1 is processed soaks under rear room temperature dry in methyl alcohol, obtains the graphite of finishing azido-.
The graphite flake of the finishing azido-of the present embodiment preparation, it is 1.6% that XPS characterizes the surface-element relative content that draws the N element.
Embodiment 5
The preparation method of this embodiment is as follows:
Step 1 in the sodium azide solution of 1mol/L, is used three-electrode system, with graphite flake as anode,, as reference electrode, with electrochemical workstation, the graphite flake electrode is applied the 2.0V constant potential and process 10min with saturated calomel electrode as negative electrode with platinum plate electrode;
Step 2, the graphite flake electrode after step 1 is processed soaks under rear room temperature dry in methyl alcohol, obtains the graphite of finishing azido-.
The graphite flake of the finishing azido-of the present embodiment preparation, it is 1.9% that XPS characterizes the surface-element relative content that draws the N element.
Embodiment 6
The preparation method of this embodiment is as follows:
Step 1 in the potassium azide solution of 2mol/L, is used three-electrode system, with graphite flake as anode,, as reference electrode, with electrochemical workstation, the graphite flake electrode is applied the 0.5V constant potential and process 60min with saturated calomel electrode as negative electrode with platinum plate electrode;
Step 2, the graphite flake electrode after step 1 is processed soaks under rear room temperature dry in methyl alcohol, obtains the graphite of finishing azido-.
The graphite flake of the finishing azido-of the present embodiment preparation, it is 1.2% that XPS characterizes the surface-element relative content that draws the N element.
Claims (6)
1. the preparation method of the graphite of a finishing azido-, is characterized in that, the method comprises the following steps:
Step 1 is in the electrolyte solution of 1～2mol/L in nitrine radical ion concentration, uses three-electrode system, with graphite flake as anode,, as reference electrode, the graphite flake electrode is applied 10～60mA continuous current process 10～60min with saturated calomel electrode as negative electrode with platinum plate electrode;
Step 2, the graphite flake electrode after step 1 is processed soaks rear dry in methyl alcohol, obtains the graphite of finishing azido-.
2. the preparation method of the graphite of finishing azido-as claimed in claim 1, is characterized in that, the electrolyte solution described in step 1 is the sodiumazide aqueous solution, the Lithium Azide aqueous solution or the potassium azide aqueous solution.
3. the preparation method of the graphite of finishing azido-as claimed in claim 1, is characterized in that, the replaceable 0.5～2V of being of the 10～60mA continuous current constant potential that in step 1, the graphite flake electrode is applied.
4. the preparation method of the graphite of finishing azido-as claimed in claim 1, is characterized in that, the electrolyte solution described in step 1 preferably adopts the sodium azide solution of 1mol/L, and the continuous current that the graphite flake electrode applies is 20mA, and the treatment time is 30min
5. the preparation method of the graphite of finishing azido-as claimed in claim 1, is characterized in that, it is the graphite flake of 2.0*2.0*0.3cm that the graphite flake described in step 1 adopts dimensions.
6. as the graphite of the finishing azido-of claim 1,2,3,4 or 5 described methods preparations.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018067455A (en) * | 2016-10-19 | 2018-04-26 | トヨタ自動車株式会社 | Lithium ion secondary battery |
| CN109715860A (en) * | 2016-09-16 | 2019-05-03 | 曼彻斯特大学 | The production of functionalized graphite's alkene |
| CN111254472A (en) * | 2018-11-30 | 2020-06-09 | 南京理工大学 | Method for electrochemically preparing copper azide/cuprous azide film |
| CN112457146A (en) * | 2019-09-06 | 2021-03-09 | 南京理工大学 | Preparation method of conductive metal organic frame packaged copper azide/cuprous azide |
| CN112662050A (en) * | 2020-12-23 | 2021-04-16 | 珠海光林新材料科技有限公司 | Heat-conducting polypropylene material and preparation method thereof |
| CN113620285A (en) * | 2021-09-08 | 2021-11-09 | 北京大学 | Method for modifying surface of graphite film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110184196A1 (en) * | 2007-01-12 | 2011-07-28 | The Board Of Trustees Of The Leland Stanford Junior University | Preparation of azide-modified carbon surfaces for coupling to various species |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110184196A1 (en) * | 2007-01-12 | 2011-07-28 | The Board Of Trustees Of The Leland Stanford Junior University | Preparation of azide-modified carbon surfaces for coupling to various species |
Non-Patent Citations (2)
| Title |
|---|
| ANANDO DEVADOSS,ET AL.: "Azide-Modified Graphitic Surfaces for Covalent Attachment of Alkyne-Terminated Molecules by "Click" Chemistry", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| ELIZABETH C. LANDIS，ET AL.: "Covalent Grafting of Redox-Active Molecules to Vertically Aligned Carbon Nanofiber Arrays via "Click" Chemistry", 《CHEMISTRY OF MATERILAS》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109715860A (en) * | 2016-09-16 | 2019-05-03 | 曼彻斯特大学 | The production of functionalized graphite's alkene |
| JP2018067455A (en) * | 2016-10-19 | 2018-04-26 | トヨタ自動車株式会社 | Lithium ion secondary battery |
| CN111254472A (en) * | 2018-11-30 | 2020-06-09 | 南京理工大学 | Method for electrochemically preparing copper azide/cuprous azide film |
| CN111254472B (en) * | 2018-11-30 | 2022-02-18 | 南京理工大学 | Method for electrochemically preparing copper azide/cuprous azide film |
| CN112457146A (en) * | 2019-09-06 | 2021-03-09 | 南京理工大学 | Preparation method of conductive metal organic frame packaged copper azide/cuprous azide |
| WO2021042921A1 (en) * | 2019-09-06 | 2021-03-11 | 南京理工大学 | Method for preparing copper azide and cuprous azide for conductive metal organic frame packaging |
| CN112457146B (en) * | 2019-09-06 | 2022-03-18 | 南京理工大学 | Preparation method of conductive metal organic frame packaged copper azide/cuprous azide |
| CN112662050A (en) * | 2020-12-23 | 2021-04-16 | 珠海光林新材料科技有限公司 | Heat-conducting polypropylene material and preparation method thereof |
| CN113620285A (en) * | 2021-09-08 | 2021-11-09 | 北京大学 | Method for modifying surface of graphite film |
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