CN108362750A - A kind of preparation method for adulterating covalent organic framework composite electrode based on gold nanoparticle - Google Patents
A kind of preparation method for adulterating covalent organic framework composite electrode based on gold nanoparticle Download PDFInfo
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Abstract
A kind of preparation method for adulterating covalent organic framework composite electrode based on gold nanoparticle, it is related to electrochemical sensor technology field, first by 1,3,5 three (4 aminophenyl benzene) and 2,5 dimethoxy terephthalaldehydes are dissolved in solvent, are reacted under the catalysis of acetic acid, and TAPB DMTP COF are obtained；It is scattered in methanol again, then sequentially adds gold chloride and sodium borohydride methanol solution is reacted, obtain Au@TAPB DMTP COF；It is dispersed through in water, obtains suspension, then modify in glassy carbon electrode surface, obtain and be based on covalent organic framework material modified glassy carbon electrode.The present invention constructs a kind of electrochemical sensor for detecting chlorogenic acid, by by Au@TAPB DMTP COF modified glassy carbon electrodes, improving the current-responsive to chlorogenic acid.
Description
Technical field
The present invention relates to electrochemical sensor field, more particularly to gold nanoparticle doping covalent organic framework modifies glass carbon
The preparation method of electrode is used in combination the modified electrode to detect chlorogenic acid.
Background technology
Chlorogenic acid is a kind of phenylpropanoids that plant generates during aerobic respiration through shikimic acid pathway.Research
Show that chlorogenic acid has pharmacological activity, have the effects that antibacterial, anti-oxidant, anti-aging, anticancer and stimulating central nervous system system,
These unique properties make chlorogenic acid medically be widely used, so it is outstanding to propose that a kind of fast and convenient method measures chlorogenic acid
It is important.
The method for being presently used for detection chlorogenic acid has：Thin-layer chromatography, high performance liquid chromatography, gas chromatography mass spectrometry and capillary electricity
Swimming method, although these detection methods have the advantages that high sensitivity, selectivity is good, detection limit is low, complicated for operation, equipment is held high
Disadvantage that is expensive, expending time length limits their application.Due to preparing simple, at low cost, quick detection and high sensitivity etc.
Advantage makes electrochemical sensor using more and more extensive.
Covalent organic framework material is the porous material of crystalline form formed by Covalent bonding together with light elements such as C, N, O, B, Si
Material, since COF has high stability, structural regularity, hole adjustability, easily functionality, to apply in gas storage, drug
The fields such as release, catalysis and photoelectricity.Gold nanoparticle has high electron density, good conductivity and high catalytic capability, these are unique
Property so that gold nanoparticle is applied in every field.
Invention content
In view of the above-mentioned problems, the present invention, which proposes a kind of gold nanoparticle, adulterates covalent organic framework material as electrode material
Material, the material modified glassy carbon electrode can effectively detect chlorogenic acid.
To achieve the above object, the present invention provides the following technical solutions：
1）Under ultrasound condition, by 1,3,5- tri- (4- aminophenyls benzene) and 2,5- dimethoxy terephthaldehyde's aldehyde monomers are dissolved in solvent
In, it is reacted under the catalysis of acetic acid, obtains TAPB-DMTP-COF；
Chemical equation is as follows：
2）Under ultrasound condition, TAPB-DMTP-COF is scattered in methanol, then sequentially adds gold chloride and sodium borohydride methanol
Solution is reacted, and Au@TAPB-DMTP-COF are obtained, and the above reaction mechanism is：
3）Under ultrasound condition, Au@TAPB-DMTP-COF are dispersed in water, obtain suspension；
4）By suspension modification in glassy carbon electrode surface, obtains and be based on covalent organic framework material decorating carbon paste electrode.
The present invention constructs a kind of electrochemical sensor for detecting chlorogenic acid, by modifying Au@TAPB-DMTP-COF
Glass-carbon electrode improves the current-responsive to chlorogenic acid.Wherein TAPB-DMTP-COF possesses big specific surface area and porous knot
Structure, the conductive good and good catalytic capability of gold nanoparticle are improved due to the synergistic effect of two kinds of materials to green original
Acid catalytic action, the sensor to the detection range of chlorogenic acid be the range of linearity be 0.01~5.0 μm of ol/ L and 5.0~
40.0 μm of ol/ L, detection are limited to 0.0095 μm of ol/ L（S/N=3）, with high sensitivity, selectivity is good, it is simple excellent to make
Point.
Further, step 1 of the present invention）Middle solvent by volume ratio be 4: 4: 1 1,4- dioxane, n-butanol and
Methanol mixing composition, two kinds of monomer solubilities are low, and solvent is very few, and monomer not readily dissolves, this ratio monomer is just completely dissolved.
The step 1）Middle elder generation after room temperature condition reacts 2h, is added acetic acid, is warming up to 70 again under the catalysis of acetic acid
It DEG C reacts again for 24 hours.First slowly polymerization generates amorphous polymer for reaction at room temperature, and assembling then occurs at high temperature and resets shape
At high crystallinity polymer.
The step 1）In, it negates the precipitation tetrahydrofuran that should be generated and after acetone washs, is dried in vacuo, obtains
TAPB-DMTP-COF solids.Since reaction is reversible, it is possible that having oligomer generation, so with tetrahydrofuran and acetone
Wash away oligomer.
The step 1）In, described 1,3,5- tri- (4- aminophenyls benzene) and 2,5- dimethoxy terephthaldehyde's aldehyde monomers
Molar ratio is 2: 3.This reaction mechanism, which is reacted for amino with aldehyde radical, generates imine linkage, 1 mole 1,3,5- tri- (4- aminophenyls
Benzene) 3 moles of amino are corresponded to, 1 mole of 2,5- dimethoxy terephthalaldehyde corresponds to 2 moles of aldehyde radicals, and aldehyde radical is 1 with amino:1 is anti-
It answers, so 1,3,5- tri- (4- aminophenyls benzene) and 2, the mixing molar ratio of 5- dimethoxy terephthalaldehydes is 2: 3.
The step 2）In, the mass ratio that feeds intake of the TAPB-DMTP-COF and gold chloride is 20: 1.Work as TAPB-DMTP-
COF and when moderate gold chloride ratio, composite material can combine TAPB-DMTP-COF bigger serfaces, high stability and gold nano
The advantages of particle satisfactory electrical conductivity, high catalytic capability, if TAPB-DMTP-COF too high levels, the electric conductivity of composite material
Difference hinders electronics transfer, if gold chloride too high levels, gold nanoparticle is reunited in COF material surfaces, and active site is reduced,
So the advantages of moderate composite material of the two ratio could cooperate with two kinds of materials.
The step 2）In, the molar ratio of the gold chloride and sodium borohydride is 1: 2.The excessive purpose of sodium borohydride is to make
Gold chloride is completely reduced into gold nanoparticle.
The step 2）In, the solid phase that negating should generate is washed with methanol, obtains Au@TAPB-DMTP-COF after drying.With
Methanol washes away the gold chloride not being reduced completely and excessive sodium borohydride.
The step 4）In, 5 μ L suspension are modified in glassy carbon electrode surface.In modified electrode, work as suspension vol
The peak current of the μ L from 2 to 5, chlorogenic acid dramatically increase, this is because the increase of chlorogenic acid enriching quantity on modified electrode.However work as
When suspension liquid measure is more than 5 μ L, the peak current of chlorogenic acid significantly reduces.This may be since excessive suspension liquid measure generation is thicker
Film reduces the electric conductivity of storeroom and hinders and transmits between electronics.
Description of the drawings
Fig. 1 is the high power transmission plot of Au@TAPB-DMTP-COF described in the embodiment of the present invention 1.
Fig. 2 is the volt-ampere curve figure of chlorogenic acid concentration and peak current described in the embodiment of the present invention 1.
Fig. 3 is the linear regression graph of chlorogenic acid concentration and peak current described in the embodiment of the present invention 1.
Specific implementation mode
One, the preparation method based on covalent organic framework material modified glassy carbon electrode：
1, the preparation of TAPB-DMTP-COF：
At room temperature, 10.5 mg 1,3,5- tri- (4- aminophenyls benzene) and 8.5 mg 2,5- dimethoxy terephthalaldehydes are weighed
Monomer puts into 4.5 mL 1,4- dioxane, n-butanol, methanol (4:4:1 v/v/v）Altogether in solution, ultrasonic half an hour makes monomer
After dissolving, 0.05 mL acetic acid is slowly added dropwise, reacts at room temperature 2h, continues that 0.45 mL acetic acid is added dropwise, puts 70 DEG C of reactions in baking oven
24h.Obtained precipitation is washed with tetrahydrofuran and acetone, is finally dried in vacuo and is obtained yellow solid for 24 hours to get 15 mg
TAPB-DMTP-COF。
2, the preparation of Au@TAPB-DMTP-COF：
At room temperature, 30mg TAPB-DMTP-COF are weighed in vial, 15mL methanol are added, ultrasonic disperse is uniform, slowly
The gold chloride that 160 μ L mass percents are 1% is added dropwise, after mixing, the sodium borohydride methanol solution of 0.02mol is added dropwise dropwise,
2h is stirred, centrifugation is washed with methanol, is finally dried in vacuo to get 25 mg Au@TAPB-DMTP-COF.
High power transmission plot Fig. 1 of the product Au@TAPB-DMTP-COF of acquirement.As seen from Figure 1：Gold nanoparticle uniformly divides
Cloth shows that Au@TAPB-DMTP-COF composite materials are successfully prepared on the surfaces TAPB-DMTP-COF.
3, the modification of glass-carbon electrode：
Glass-carbon electrode is first polished to minute surface with alumina powder, is rinsed with water totally, then is cleaned by ultrasonic with ethyl alcohol and nitric acid, nitrogen is used
Air-flow dries up electrode surface, obtains the glass-carbon electrode of clean surface.
It takes 1mg Au@TAPB-DMTP-COF to put into 1mL water, after ultrasonic disperse 2h, obtains suspension.
5 μ L hanging drops are added in clean glassy carbon electrode surface, are put into drier drying to get Au@TAPB-DMTP-
The glass-carbon electrode of COF modifications, that is, be based on covalent organic framework material decorating carbon paste electrode.
Two, test result measures：
1. by electrolytic cell clean drying wash with distilled water after 10% nitric acid dousing 12h.Accurately pipette 10mL 0.1M phosphoric acid
Buffer solution（pH=7）Into electrolytic cell, chlorogenic acid standard liquid is added and prepares various concentration standard solution, and be put into one it is clean
Magneton is uniformly mixed so as to solution.
2. traditional three-electrode system is used, using the glass-carbon electrode of Au@TAPB-DMTP-CO modifications as working electrode,
Ag/AgCl electrodes are used as to electrode as reference electrode, platinum electrode, three-electrode system are connect with electrochemical workstation.
3. differential pulse voltammetry detection process：Turn off after the completion of the deposition voltage stirring enrichment 120s of 0.2V, deposition
Stirring stands 20s, and 0 V of initial potential is then arranged, and terminates current potential 0.4V, and current potential increment is 0.01V, and impulse amplitude is
0.1V, pulse width 1.0s, pulse spacing 0.2s record Stripping Voltammetry curve.
4. repeating above step 1,2,3, chlorogenic acid is formulated as 0.01,0.05,0.1,0.3,0.5,0.7,1,2,3,5,
7,10,20,30 and 40 μM, chlorogenic acid differential pulse voltammetry curve is recorded, linear regression graph is done with peak current-chlorogenic acid concentration.
From the chlorogenic acid concentration of Fig. 2 and the volt-ampere curve figure of peak current：Curve 1 to 15 therein respectively represents
0.01, the relationship of 0.05,0.1,0.3,0.5,0.7,1,2,3,5,7,10,20,30 and 40 μM of chlorogenic acid concentration and current strength,
Current strength illustrates that the modified electrode has significant current-responsive to chlorogenic acid as the concentration of chlorogenic acid increases and increases.
From the chlorogenic acid concentration of Fig. 3 and the linear regression graph of peak current：Au@TAPB-DMTP-COF modified electrodes are examined
The differential pulse voltammetry curve for surveying the chlorogenic acid of various concentration is continuously increased two sections of presentation linearly with detectable substance concentration：
0.01-5.0μmol/ L：Ipa (μA) = 0.1660C (μmol/ L) + 0.09 (R2=0.998)；
5.0-40.0μmol/ L：Ipa (μA) = 0.0747C (μmol/ L) + 0.607 (R2 =0.994)。
First segment is mainly linearly absorption and control process, and second segment is linearly mass transfer diffusion process. Au@TAPB-DMTP-
The detection of COF sensors is limited to 0.0095 μm of ol/ L（S/N=3）.
Therefore：Had using electrochemical gaging chlorogenic acid of the present invention and prepares low excellent of simple, high sensitivity, detection limit
Point.
Claims (9)
1. a kind of preparation method for adulterating covalent organic framework composite electrode based on gold nanoparticle, it is characterised in that including
Following steps：
1）Under ultrasound condition, by 1,3,5- tri- (4- aminophenyls benzene) and 2,5- dimethoxy terephthalaldehydes are dissolved in solvent,
It is reacted under the catalysis of acetic acid, obtains TAPB-DMTP-COF；
2）Under ultrasound condition, TAPB-DMTP-COF is scattered in methanol, then sequentially adds gold chloride and sodium borohydride methanol
Solution is reacted, and Au@TAPB-DMTP-COF are obtained；
3）Under ultrasound condition, Au@TAPB-DMTP-COF are dispersed in water, obtain suspension；
4）By suspension modification in glassy carbon electrode surface, obtains and be based on covalent organic framework material modified glassy carbon electrode.
2. preparation method according to claim 1, it is characterised in that the step 1）Middle solvent is 4: 4: 1 by volume ratio
1,4- dioxane, n-butanol and methanol mixing composition.
3. preparation method according to claim 1, it is characterised in that the step 1）Middle elder generation is under the catalysis of acetic acid in room
After warm conditioned response 2h, acetic acid is added again, is warming up to 70 DEG C and reacts again for 24 hours.
4. preparation method according to claim 3, it is characterised in that the step 1）In, the precipitation that should generate is negated with four
After hydrogen furans and acetone washing, vacuum drying obtains TAPB-DMTP-COF solids.
5. preparation method according to claim 1, it is characterised in that the step 1）In, described 1,3,5- tri- (4- amino
Phenyl benzene) and 2,5- dimethoxy terephthalaldehydes molar ratio be 2: 3.
6. preparation method according to claim 1, it is characterised in that the step 2）In, the TAPB-DMTP-COF and
The mass ratio that feeds intake of gold chloride is 20: 1.
7. preparation method according to claim 6, it is characterised in that the step 2）In, the gold chloride and sodium borohydride
Molar ratio be 1: 2.
8. preparation method according to claim 6, it is characterised in that the step 2）In, the solid phase that should be generated is negated with first
Alcohol washs, and obtains Au@TAPB-DMTP-COF after drying.
9. preparation method according to claim 1, it is characterised in that the step 4）In, 5 μ L suspension are modified in glass
Carbon electrodes.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104195042A (en) * | 2014-07-27 | 2014-12-10 | 北京化工大学 | Preparation method and application of nano material monolithic column immobilized enzyme biological micro-reactor |
| CN104624160A (en) * | 2015-01-21 | 2015-05-20 | 北京科技大学 | Preparation method of thermal conduction enhanced metal organic framework gas storage material |
-
2018
- 2018-03-07 CN CN201810186011.1A patent/CN108362750B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104195042A (en) * | 2014-07-27 | 2014-12-10 | 北京化工大学 | Preparation method and application of nano material monolithic column immobilized enzyme biological micro-reactor |
| CN104624160A (en) * | 2015-01-21 | 2015-05-20 | 北京科技大学 | Preparation method of thermal conduction enhanced metal organic framework gas storage material |
Non-Patent Citations (2)
| Title |
|---|
| XIAOFEI SHI等: "Imparting Catalytic Activity to a Covalent Organic Framework Material by Nanoparticle Encapsulation", 《ACS APPL. MATER. INTERFACES》 * |
| 刘婷知: "基于共价有机框架材料的电化学传感器的构建", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》 * |
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