CN103382130A - Glassy carbon material with surface modified by azido groups and preparation method thereof - Google Patents
Glassy carbon material with surface modified by azido groups and preparation method thereof Download PDFInfo
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- CN103382130A CN103382130A CN201310253511XA CN201310253511A CN103382130A CN 103382130 A CN103382130 A CN 103382130A CN 201310253511X A CN201310253511X A CN 201310253511XA CN 201310253511 A CN201310253511 A CN 201310253511A CN 103382130 A CN103382130 A CN 103382130A
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Abstract
The invention discloses a glassy carbon material 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 0.5-2 mol/L, employing a three-electrode system, with a glassy carbon sheet as an anode, a platinum sheet as a cathode and a saturated calomel electrode as a reference electrode, treating the glassy carbon sheet electrode by applying a constant electric potential of 0.5-1 V for 10-30 min; and soaking the treated glassy carbon sheet electrode in methanol, and then drying at the room temperature to obtain the glassy carbon sheet with the surface modified by the azido groups. The method has high selectivity, does not introduce other groups or atoms onto the surface, requires no cooling conditions for the reaction, has raw materials with low price, employs no organic solvent, and only needs one-step reaction; and the method has the advantages of reliability, high efficiency and high selectivity, and thereby having good application prospects in electrochemical experiments or electroanalytical chemistry.
Description
Technical field
The invention belongs to the materials chemistry field, relate to a kind of method that glass carbon material surface is modified azido-, and the glass carbon material that utilizes the finishing azido-of the method preparation.
Background technology
The advantage of glass carbon material is good conductivity, and chemical stability is high, and the electromotive force scope of application is wide, can be made into the electrode shapes such as cylinder, disk, obtains increasingly extensive application in electrochemistry experiment or electroanalytical chemistry.Similar other electrode materials in order to enlarge its range of application, need to carry out finishing to it.Electrode modification is to carry out molecular designing in electrode material surface, and the forms such as molecule, ion, polymkeric substance and chemical film that will have certain character are fixed on electrode surface, make it have certain specific chemistry and electrochemical properties.Electrode modification has been expanded electrochemical research field, has been applied at present all many-sides such as life, environment, the energy, analysis, electronics and materialogy.The electrode materials that wherein is modified with azido-has caused people's concern, because can utilize the click chemistry method of its end azido-and alkynyl that electroactive substance or other functional moleculars are modified material surface; Be a kind of method that realizes the link of multiple structure of functional groups, have advantages of reliable, efficient and selectivity is high.
Equally, modify azido-and cause too people's concern on the glass carbon material, US Patent No. 20110184196 discloses a kind of method of directly modifying azido-on the glass carbon material, the method is by reacting at low temperatures the generation iodazide at existing preparation iodine monochloride and sodiumazide at the anhydrous acetonitrile solvent, and then reaction solution obtains the finished product with the reaction of glass carbon material again.The method weak point is: make a certain amount of iodine also be modified at the glass carbon 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
For the problem that exists in the middle of above-mentioned prior art, the object of the invention is, provides a kind of and can solely azido-be connected to the method for glass carbon material surface, and utilized the glass carbon material of the finishing azido-of the method preparation; The method is simple and cost is low.
In order to realize above-mentioned task, the scheme that the present invention adopts is:
A kind of preparation method of glass carbon material of finishing azido-, the method comprises the following steps:
Step 1 is in 0.5～2mol/L electrolyte solution in nitrine radical ion concentration, uses three-electrode system, with the glass carbon plate as anode,, as reference electrode, glass carbon plate electrode is applied 0.5～1V constant potential process 10～30min with saturated calomel electrode as negative electrode with platinized platinum;
Step 2, the glass carbon plate electrode after step 1 is processed soaks rear dry in methyl alcohol, obtains the glass carbon material of finishing azido-.
A kind of glass carbon material that utilizes the finishing azido-of aforesaid method preparation.
Further, the electrolyte solution described in step 1 adopts the sodiumazide aqueous solution, the Lithium Azide aqueous solution or the potassium azide aqueous solution.
Preferably, the electrolyte solution described in step 1 preferably adopts the sodium azide solution of 1mol/L, and to the preferred 0.6V of constant potential that glass carbon plate electrode applies, the treatment time is 20min.
It is the glass carbon plate of 2.0*2.0*0.3cm that glass carbon plate described in step 1 adopts dimensions.
In the present invention, the method for glass carbon material surface modification azido-has highly selective, does not introduce other group or atom to the surface, and reaction need not cooling conditions, and cost of material is cheap, not with an organic solvent, only needs single step reaction; Have reliable, efficient and the high advantage of selectivity has a good application prospect in electrochemistry experiment or electroanalytical chemistry.
Description of drawings
Fig. 1 is the X-photoelectron spectrum figure that the table of embodiment 1 preparation is modified the glass carbon plate of azido-;
Fig. 2 is the X-photoelectron spectrum figure N1s high resolution X-photoelectron spectrum figure of glass carbon plate of the finishing azido-of embodiment 1 method preparation;
Fig. 3 is the Infrared Reflective Spectra figure of glass carbon plate of the finishing azido-of embodiment 1 preparation;
Embodiment
The present invention is to contain electric nitrine root (N with the method that azido-is modified at the glass carbon material surface
3 -) the aqueous solution in, take the glass carbon plate as anode, apply constant potential, utilize nitrine root and glass carbon plate surface that electrochemical reaction occurs azido-be connected on glass carbon plate surface, concrete steps are as follows:
Step 1 is in 0.5～2mol/L electrolyte solution in nitrine radical ion concentration, uses three-electrode system, with the glass carbon plate as anode,, as reference electrode, glass carbon plate electrode is applied 0.5～1V constant potential process 10～30min with saturated calomel electrode as negative electrode with platinized platinum;
Step 2, the glass carbon plate electrode after step 1 is processed soaks rear dry in methyl alcohol, obtains the glass carbon material of finishing azido-.
Electrolyte solution described in step 1 adopts the sodiumazide aqueous solution, the Lithium Azide aqueous solution or the potassium azide aqueous solution; In described three-electrode system, negative electrode can also adopt nickel sheet, copper sheet etc.
Described glass carbon plate is the sheet glass carbon that the glass carbon material is made, and the preferred size specification of glass carbon plate is 2.0*2.0*0.3cm, and namely length and width is 2cm, thickness is the glass carbon plate of 0.3cm, or is chosen in size less than the glass carbon plate 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 glass carbon material of finishing azido-, the method comprises the following steps:
Step 1 in the sodium azide solution of 1mol/L, is used three-electrode system,, as negative electrode,, by electrochemical workstation, glass carbon plate electrode is applied the 0.6V constant potential and processes 20min as reference electrode with saturated calomel electrode with platinized platinum as anode with the glass carbon plate;
Step 2, the glass carbon plate electrode after step 1 is processed soaks in methyl alcohol removes surface impurity, then lower dry in room temperature (25 ℃), obtains the glass carbon material of finishing azido-.
Fig. 1 and Fig. 2 are respectively the X-photoelectron spectrum full figure scanning of glass carbon plate 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 Reflective Spectra figure of glass carbon plate of the finishing azido-of embodiment 1 preparation; The as can be seen from the figure infrared absorption 2100cm of azido-
-1The absorption peak of left and right, the CO2 signal of 2350cm-1 two of left and right absorption peak for adsorbing.
By above sign, can see that azido-successfully modifies on the glass carbon plate, and not introduce other elements, it is 1.8% 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,, as negative electrode,, by electrochemical workstation, glass carbon plate electrode is applied the 0.8V constant potential and processes 10min as reference electrode with saturated calomel electrode with platinized platinum as anode with the glass carbon plate;
Step 2, the glass carbon plate electrode after step 1 is processed soaks in methyl alcohol removes surface impurity, then at room temperature dry, obtains the glass carbon material of finishing azido-.
The glass carbon material of the finishing azido-of the present embodiment preparation, it is 1.0% 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 the glass carbon plate as anode,, as reference electrode, by electrochemical workstation, glass carbon plate electrode is applied the 1.0V constant potential and process 30min with saturated calomel electrode as negative electrode with platinized platinum;
Step 2, the glass carbon plate electrode after step 1 is processed soaks in methyl alcohol removes surface impurity, then at room temperature dry, obtains the glass carbon material of finishing azido-.
The glass carbon material 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 4
The preparation method of this embodiment is as follows:
Step 1 in the sodium azide solution of 0.5mol/L, is used three-electrode system, with the glass carbon plate as anode,, as reference electrode, by electrochemical workstation, glass carbon plate electrode is applied the 0.5V constant potential and process 30min with saturated calomel electrode as negative electrode with platinized platinum;
Step 2, the glass carbon plate electrode after step 1 is processed soaks in methyl alcohol removes surface impurity, then at room temperature dry, obtains the glass carbon material of finishing azido-.
The glass carbon material 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.
Claims (5)
1. the preparation method of the glass carbon material of a finishing azido-, is characterized in that, the method comprises the following steps:
Step 1 is in 0.5～2mol/L electrolyte solution in nitrine radical ion concentration, uses three-electrode system, with the glass carbon plate as anode,, as reference electrode, glass carbon plate electrode is applied 0.5～1V constant potential process 10～30min with saturated calomel electrode as negative electrode with platinized platinum;
Step 2, the glass carbon plate electrode after step 1 is processed soaks rear dry in methyl alcohol, obtains the glass carbon material of finishing azido-.
2. the preparation method of the glass carbon material of finishing azido-as claimed in claim 1, is characterized in that, the electrolyte solution described in step 1 adopts the sodiumazide aqueous solution, the Lithium Azide aqueous solution or the potassium azide aqueous solution.
3. the preparation method of the glass carbon material of finishing azido-as claimed in claim 1, it is characterized in that, electrolyte solution described in step 1 preferably adopts the sodium azide solution of 1mol/L, and to the preferred 0.6V of constant potential that glass carbon plate electrode applies, the treatment time is 20min.
4. the preparation method of the glass carbon material of finishing azido-as claimed in claim 1, is characterized in that, it is the glass carbon plate of 2.0*2.0*0.3cm that the glass carbon plate described in step 1 adopts dimensions.
5. as the glass carbon material of the finishing azido-of claim 1,2,3 or 4 described methods preparations.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254472A (en) * | 2018-11-30 | 2020-06-09 | 南京理工大学 | Method for electrochemically preparing copper azide/cuprous azide film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775088A (en) * | 2009-01-13 | 2010-07-14 | 清华大学 | Azide or terminal alkynyl modified polystyrene resin and preparation method thereof |
| 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 (2)
| 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 |
| CN101775088A (en) * | 2009-01-13 | 2010-07-14 | 清华大学 | Azide or terminal alkynyl modified polystyrene resin and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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