CN104614425B - A kind of functionalized carbon nano-tube carries Cu2The preparation and application of O hexagram crystallite composites - Google Patents
A kind of functionalized carbon nano-tube carries Cu2The preparation and application of O hexagram crystallite composites Download PDFInfo
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- CN104614425B CN104614425B CN201510028126.4A CN201510028126A CN104614425B CN 104614425 B CN104614425 B CN 104614425B CN 201510028126 A CN201510028126 A CN 201510028126A CN 104614425 B CN104614425 B CN 104614425B
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Abstract
Cu is carried the invention provides a kind of functionalized carbon nano-tube with high miller index surface structure2The preparation method of O hexagram crystallite composites, with PEDOT functionalization MWCNTs as carrier, not only can substantially reduce Cu2The size of O hexagram crystallites, improves Cu2The decentralization and utilization ratio of O catalysed particulates, also help the electro transfer between glucose and composite catalyst, significantly enhance PEDOT functionalization MWCNTs and carry Cu2The O hexagram crystallite composites electro catalytic activity glycoxidative to grape, so that showing excellent detection performance without enzyme electrochemical glucose sensor by what the composite built.Sensor preparation process is simple in the present invention, and there is the range of linearity wider, relatively low test limit and good reappearance, stability and antijamming capability to glucose detection, had a good application prospect in fields such as clinical diagnosis, food industry analyses.
Description
Technical field
The present invention relates to electrochemical sensor field, specifically a kind of functionalized carbon nano-tube carries Cu2O hexagram crystallites
The preparation and application of composite.
Background technology
In recent years, the research to electrochemical glucose sensor causes increasing concern, how to prepare sensitivity
It is high, the selectivity good, response time is short, the range of linearity is wide, the electrochemical glucose sensor of stability and favorable reproducibility is so far
Study hotspot.The glucose sensor of report mainly has enzyme fundamental mode and without two kinds of enzyme type at present, although enzyme fundamental mode sensor exists
Have during glucose detection enzyme in good selectivity and sensitivity, but enzyme electrode by external environment such as temperature, pH etc. because
The influence of element is larger, and unstable and easy in inactivation directly affects the life-span of sensor and the accuracy of measurement result, in certain journey
The use of enzyme electrode is constrained on degree.Therefore, having without enzyme type electrochemical glucose sensor for superior performance is built very heavy
The meaning wanted.
Cu oxide（Including Cu2O and CuO）Micro-/ nano particle is due to catalytic performance is high, cheap and environment
Friendly the features such as and be taken seriously in electrochemical sensor research field.On the other hand, the electrocatalysis characteristic of micro-/ nano particle is strong
Strong to depend on its shape and surface atom arrangement architecture, the micro-/ nano particle with high miller index surface structure typically exhibits height
Electrocatalysis characteristic.Although having more document report at present using Cu oxide micro-/ nano particle structure without enzyme type
Electrochemical glucose sensor, but shape controlled synthesis about Cu oxide micro-/ nano particle and use it for electrochemistry Portugal
Research Literature report prepared by grape sugar sensor is few, relates generally to several following document reports：(1) 2009 year
《Electrochemistry Communications》Report porous C u2The micro- cube modified electrodes of O are used for H2O2And grape
Sugared detects without enzyme；(2) 2013 years《Biosensors and Bioelectronics》Report a kind of based on Cu2O nanometers
The electrochemical sensor of cube/graphene composite material is used for H2O2Detected without enzyme with glucose；(3) 2013 years
《Talanta》Report and sensed without enzyme electrochemical glucose based on CuO nanoneedles/graphene/carbon nanofiber modified electrode
Device；(4) 2013 years《Sensors》Report the synthesis of CuO nanometer sheet and its answering in glucose is without enzyme Electrochemical Detection
With；(5) 2014 years《Sensors and Actuators B》Then report it is a kind of based on CuO nano wires without enzyme electrochemistry Portugal
Grape sugar sensor.However, the above-mentioned variously-shaped Cu oxide micro-/ nano particle crystal plane structure without high index, has
Close the functionalized carbon nano-tube with high miller index surface structure and carry Cu2The shape controlled synthesis of O hexagram crystallite composites
And it is applied to the research in electrochemical sensor field there is not yet document and patent report.
The content of the invention
Cu is carried it is an object of the invention to provide a kind of simple and effective functionalized carbon nano-tube2O hexagrams crystallite is combined
The preparation method of material and using the composite build can meet actually detected needs without enzyme type electrochemical glucose sensing
Device.
Realizing the technical scheme of the object of the invention is：
A kind of functionalized carbon nano-tube carries Cu2The preparation of O hexagram crystallite composites, comprises the following steps：
（1）The multi-walled carbon nano-tubes for adding 20 mg to be acidified in equipped with 20 mL, tri- containers of distilled water（MWCNTs）、
Lauryl sodium sulfate（SDS）With 5~200 μ L 3,4- ethene dioxythiophenes（EDOT）Monomer, stirs after 2 h dropwise at room temperature
Add 100 mg mL−1Ammonium persulfate aqueous solution, then continuously stir 24 h, products therefrom is through centrifugation, washing and is vacuum dried
Afterwards, poly- 3,4-rthylene dioxythiophene is obtained（PEDOT）Functionalization MWCNTs carrier materials；
（2）1 g polyvinylpyrrolidones are added in 13 mL, tri- distilled water（PVP）, and by Cu/PEDOT functionalization
The mass ratio of MWCNTs=1/4 adds PEDOT functionalization MWCNTs and 2 mg mL−1CuSO4Solution, after the h of magnetic agitation 2
Add the mixed solution of trisodium citrate and sodium carbonate（Concentration is 0.6 M）, continue to add 2 mL 0.1 after stirring 10 min
The glucose solution of~2 M, then continuously stirs 10 min~24 h of reaction at 40~120 DEG C of oil bath, products therefrom pass through from
After the heart, washing and vacuum drying, obtain PEDOT functionalization MWCNTs and carry Cu2O hexagram crystallite composites.
A kind of functionalized carbon nano-tube carries Cu2The application of O hexagram crystallite composites, by Nafion by PEDOT
Functionalization MWCNTs carries Cu2O hexagram crystallite composites are modified in glass-carbon electrode（GCE）On construct a kind of new being used for
The detection of glucose without enzyme type electrochemical glucose sensor.
The advantage or beneficial effect of the application：
According to the present invention, with PEDOT functionalization MWCNTs as carrier, Cu not only can be substantially reduced2O hexagram crystallites
Size, improve Cu2The decentralization and utilization ratio of O catalysed particulates, also help between glucose and composite catalyst
Electro transfer, significantly enhance PEDOT functionalization MWCNTs carry Cu2O hexagram crystallite composites are to grape glycosyloxy
The electro catalytic activity of change, so that showing excellent inspection without enzyme electrochemical glucose sensor by what the composite built
Survey performance.Composite and the sensor preparation process is simple prepared with composite in the present invention, and have to glucose detection
Have the range of linearity wider, relatively low test limit and good reappearance, stability and antijamming capability, clinical diagnosis,
The fields such as food industry analysis have a good application prospect.
Brief description of the drawings
Fig. 1 carries Cu to prepare PEDOT functionalized carbon nano-tubes2The block diagram of O hexagram crystallite composites.
Fig. 2 is the block diagram for preparing electrochemical glucose sensor.
Specific embodiment
Embodiment：Prepare a kind of functionalized carbon nano-tube and carry Cu2O hexagram crystallite composites.
Referring to Figures 1 and 2, (1) added in equipped with 20 mL, tri- containers of distilled water 20 mg be acidified MWCNTs,
Lauryl sodium sulfate（SDS）With 5~200 μ L 3,4- ethene dioxythiophenes（EDOT）Monomer, stirs after 2 h dropwise at room temperature
Add 100 mg mL−1Ammonium persulfate aqueous solution, then continuously stir 24 h, products therefrom is through centrifugation, washing and is vacuum dried
Afterwards, PEDOT functionalization MWCNTs carrier materials are obtained；
(2) 1 g polyvinylpyrrolidones are added in 13 mL, tri- distilled water（PVP）, and by Cu/PEDOT functionalization
The mass ratio of MWCNTs=1/4 adds PEDOT functionalization MWCNTs and 2 mg mL−1CuSO4Solution, after the h of magnetic agitation 2
Add the mixed solution of trisodium citrate and sodium carbonate（Concentration is 0.6 M）, continue to add 2 mL 0.1 after stirring 10 min
The glucose solution of~2 M, then continuously stirs 10 min~24 h of reaction at 40~120 DEG C of oil bath, products therefrom pass through from
After the heart, washing and vacuum drying, obtain PEDOT functionalization MWCNTs and carry Cu2O hexagram crystallite composites；
The electrochemical glucose sensor of detection glucose is prepared with composite, by Nafion by PEDOT functionalization
MWCNTs carries Cu2O hexagram crystallite composites are modified in glass-carbon electrode（GCE）On construct a kind of new detection glucose
Without enzyme type electrochemical glucose sensor.
Product checking：Electro-chemical test shows that prepared PEDOT functionalization MWCNTs carries Cu2O hexagrams crystallite is answered
The condensation material electro catalytic activity glycoxidative to grape carries Cu apparently higher than acidifying MWCNTs2O hexagrams crystallite and it is carried on
Other different shapes Cu on PEDOT functionalization MWCNTs2O crystallites.
The constructed detection without enzyme electrochemical glucose sensor to glucose has the range of linearity wider（0.495
μM~0.374 mM and 0.374 mM~3.446 mM）, relatively low test limit（0.04 μM）And good reappearance（It is parallel
Determine 7 times, RSD is 4.6%）, stability（Response current still keeps original 82.9% after 28 days）And antijamming capability（Smart ammonia
The common interference thing such as acid, hydrogen peroxide, ascorbic acid, uric acid, dopamine, sodium chloride has not significant impact to glucose detection）.
In electrochemical sensor modified electrode the size of Cu oxide micro-/ nano particle, decentralization and electrocatalysis characteristic with
Carrier material and its surface nature used is closely related.Inventor's discovery, with PEDOT functionalization MWCNTs as carrier, not only
Cu can substantially be reduced2The size of O hexagram crystallites, improves Cu2The decentralization and utilization ratio of O catalysed particulates, also help
Electro transfer between glucose and composite catalyst.Meanwhile, with reference to Cu2The high index that O hexagram crystallites have
The features such as crystal plane structure, significantly enhance PEDOT functionalization MWCNTs and carry Cu2O hexagram crystallite composites are to grape
Glycoxidative electro catalytic activity, so that showing excellent inspection by the electrochemical glucose sensor that the composite builds
Survey performance.
The present invention is prepared for high index with PEDOT functionalization MWCNTs as carrier using simple chemical reduction method
The PEDOT functionalization MWCNTs of crystal plane structure carries Cu2O hexagram crystallite composites, and one kind is constructed on this basis
It is new without enzyme type electrochemical glucose sensor.
Claims (3)
1. a kind of functionalized carbon nano-tube carries Cu2The preparation method of O hexagram crystallite composites, it is characterized in that：Including as follows
Step：
（1）MWCNTs, the lauryl sodium sulfate for adding 20 mg to be acidified in equipped with 20 mL, tri- containers of distilled water
（SDS）With 5~200 μ L 3,4- ethene dioxythiophenes（EDOT）Monomer, 100 mg mL are added dropwise over after 2 h are stirred at room temperature -1Ammonium persulfate aqueous solution, then continuously stir 24 h, after products therefrom is through centrifugation, washing and vacuum drying, obtain PEDOT work(
MWCNTs carrier materials can be changed；
（2）1 g polyvinylpyrrolidones are added in 13 mL, tri- distilled water（PVP）, and by Cu/PEDOT functionalization
The mass ratio of MWCNTs=1/4 adds PEDOT functionalization MWCNTs and 2 mg mL-1CuSO4Solution, after the h of magnetic agitation 2
The mixed solution that concentration is 0.6 M trisodium citrates and concentration is 0.6 M sodium carbonate is added, continues to add 2 after stirring 10 min
The glucose solution of the M of mL 0.1~2, then continuously stirs 10 min~24 h of reaction at 40~120 DEG C of oil bath, and gained is produced
After thing is through centrifugation, washing and vacuum drying, obtains PEDOT functionalization MWCNTs and carry Cu2O hexagram crystallite composites.
2. functionalized carbon nano-tube obtained in preparation method according to claim 1 carries Cu2O hexagram crystallite composite woods
Expect in preparation without the application in enzyme type electrochemical glucose sensor, it is characterized in that：By Nafion by PEDOT functionalization
MWCNTs carries Cu2O hexagram crystallite composites are modified in glass-carbon electrode（GCE）On construct it is a kind of for glucose detection
Without enzyme type electrochemical glucose sensor.
3. application according to claim 2, it is characterized in that：It is constructed without enzyme type electrochemical glucose sensor to Portugal
The detection range of linearity of grape sugar：0.495 μM~0.374 mM and 0.374 mM~3.446 mM, test limit：0.04 μM and
Good reappearance：Parallel determination 7 times, RSD is 4.6%, stability：Response current still keeps original 82.9% and anti-after 28 days
Interference performance：Arginine, hydrogen peroxide, ascorbic acid, uric acid, dopamine, sodium chloride have not significant impact to glucose detection.
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| CN107029709B (en) * | 2017-04-20 | 2020-04-03 | 河南科技学院 | TiO 22Preparation method of supported high-index crystal face icosahedron-shaped nano Ag photocatalyst |
| CN107008258B (en) * | 2017-04-20 | 2019-07-05 | 河南科技学院 | TiO2Application of the nanometer Ag photochemical catalyst of load in degradation of phenol |
| CN108680625A (en) * | 2018-05-07 | 2018-10-19 | 杭州电子科技大学 | The preparation method and applications of cuprous oxide/cobalt acid nickel hollow-core construction composite nano-microsphere |
| CN109387552B (en) * | 2018-10-12 | 2021-04-16 | 温州大学 | Copper-based porous carbon microsphere composite material and preparation method and application thereof |
| CN110302792B (en) * | 2019-07-15 | 2021-09-24 | 广西师范大学 | Carbon nanotube-loaded NiCoO in non-enzymatic electrochemical glucose sensingxPreparation method and application of composite material catalyst |
| CN112195355B (en) * | 2020-10-12 | 2021-10-15 | 昆明理工大学 | Metal matrix composite material with carbon nanotubes distributed in hexagon and preparation method thereof |
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