CN106053561B - Nano-graphene-carbon nanotube-ionic liquid composite membrane and its preparation and application - Google Patents
Nano-graphene-carbon nanotube-ionic liquid composite membrane and its preparation and application Download PDFInfo
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Abstract
The invention discloses a kind of nano-graphene carbon nanotube ionic liquid composite membrane and its preparation and application, the thickness of the nano-graphene carbon nanotube ionic liquid composite membrane is 4000nm to 6000nm, the nano-graphene carbon nanotube ionic liquid composite membrane is overlapped mutually by multiple graphene sheet layers to be formed, and the spacing between adjacent two graphene sheet layers is 20nm~50nm；Monodispersed has carbon nanotube and ionic liquid between two adjacent graphene sheet layers.Composite membrane specific surface area of the present invention is high, and the composite membrane has good electro-chemical activity, can be widely applied to nano electro-catalytic field and field of biosensors, and detection sensitivity is high.
Description
Technical field
The invention belongs to field of nanometer material technology, more particularly, to a kind of nano-graphene-carbon nanotube-ionic liquid
Composite membrane and its preparation and application, the composite membrane are the composite membrane of nano-graphene-carbon nanotube-ionic liquid.
Background technology
Graphene (Graphene) is a kind of unique two-dimentional carbon nanomaterial, because its with good electricity, mechanics and
Thermal property (140 times of electron mobility higher than silicon, 100 times of tensile strength higher than same thickness steel alloy and high is led
Hot coefficient etc.), good biocompatibility, the chemically and thermally mechanical stability of cheap synthesis cost and superelevation exists in recent years
Microelectronics, new superconduction material, energy storage, sensor and electro-catalysis etc. have broad application prospects.
Graphene can not only show itself special property, but also be expected to be assembled into novel as two-dimension nano materials
The thin-film material of macroscopic view.According to current document report, spin coating and dip coating, suction filtration and evaporation induced self-assembly method can be passed through
Deng by graphene directional assembly at graphene film.Obtained graphene film is high-sequential from microcosmic and accumulation is close
Nanometer laminated structure, the important parameters such as thickness, the Nomenclature Composition and Structure of Complexes of film can accurately control.However simple graphene film
There is stronger pi-pi bond to act between nano-graphene lamella so that graphene nano lamella is easy to heap, to reduce graphite
The specific surface area of alkene film reduces the mass transfer space of ion, reduces its conductivity, and then the electrochemistry for influencing graphene film itself is lived
Property.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the purpose of the present invention is to provide a kind of nano-graphenes-
Carbon nanotube-ionic liquid composite membrane and its preparation and application are prepared wherein by composition and structure to composite membrane key
Crucial raw material proportioning, processing procedure etc. are improved in method, can effectively solve the problem that graphene nano compared with prior art
Lamella easily heaps the problem for causing graphene film specific surface area low, and the composite membrane has good electro-chemical activity, can be wide
General to be applied to nano electro-catalytic field and field of biosensors, detection sensitivity is high.
To achieve the above object, according to one aspect of the present invention, provide a kind of nano-graphene-carbon nanotube-from
Sub- liquid composite membrane, which is characterized in that the thickness of the nano-graphene-carbon nanotube-ionic liquid composite membrane be 4000nm extremely
6000nm, which is overlapped mutually by multiple graphene sheet layers and is formed, adjacent
Two graphene sheet layers between spacing be 20nm~50nm；Monodispersed between two adjacent graphene sheet layers
There are carbon nanotube and ionic liquid.
Preferably, the ionic liquid is 1- butyl -3- methyl imidazolium tetrafluoroborates or 1- butyl -3- methylimidazoles six
Fluorophosphate.
It is described in the nano-graphene-carbon nanotube-ionic liquid composite membrane as present invention further optimization
The mass ratio of both graphene and the carbon nanotube is 2~4.
It is another aspect of this invention to provide that providing a kind of system of nano-graphene-carbon nanotube-ionic liquid composite membrane
Preparation Method, which is characterized in that include the following steps：
(1) it is ground to obtain mixture after mixing graphene oxide, carbon nanotube and ionic liquid, then, then will
The mixture is dispersed in water, and forms the oxidation that the sum of both graphene oxide and carbon nanotube concentration is 4mg/ml~6mg/ml
Graphene-carbon nano tube-ionic liquid mixed liquor；
(2) take the graphene oxide-carbon nanotube-ionic liquid that step described in 100ml~200ml (1) obtains mixed
Liquid is closed, is separated by solid-liquid separation by the vacuum filtration instrument with filter membrane, isolated solid divides through drying and with the filter membrane
Nano graphene oxide-carbon nanotube-ionic liquid composite membrane is obtained from rear；
(3) nano graphene oxide-carbon nanotube-ionic liquid composite membrane hydrogen for obtaining the step (2)
Acid iodide reduction obtains nano-graphene-carbon nanotube-ionic liquid composite membrane.
As present invention further optimization, the graphene oxide in the step (1) is to prepare oxygen using Hummers methods
The aqueous solution of graphite alkene then obtains graphene oxide after being freeze-dried the aqueous solution of the graphene oxide.
As present invention further optimization, graphene oxide described in the step (1), the carbon nanotube and described
The proportioning of ionic liquid three is 1mg:(0.25mg~0.5mg):(5 μ l of μ l~10).
As present invention further optimization, the ionic liquid in the step (1) is 1- butyl -3- methylimidazole tetrafluoros
Borate.
As present invention further optimization, the water in the step (1) is ultra-pure water.
As present invention further optimization, the graphene oxide-carbon nanotube-ionic liquid in the step (1)
Body mixed liquor also passes through ultrasonic disperse and handles.
Another aspect according to the invention provides and utilizes above-mentioned nano-graphene-carbon nanotube-ionic liquid composite membrane
Nano-graphene-carbon nanotube-ionic liquid composite membrane for being prepared of preparation method detection heavy metal ion application.
As present invention further optimization, the heavy metal ion is cadmium ion or lead ion.
Above-mentioned nano-graphene-carbon nanotube-ionic liquid composite membrane is utilized it is another aspect of this invention to provide that providing
Nano-graphene-carbon nanotube-ionic liquid composite membrane for being prepared of preparation method in no enzyme type hydrogen peroxide electrochemistry
The application of sensor.
Contemplated above technical scheme through the invention, compared with prior art, due to the raw material in preparation method
Proportioning, treatment process process etc. are improved, and the inside composition and structure of the composite membrane being prepared also change accordingly,
Form the structure of composite membrane with high-specific surface area, high electrochemical activity.
Nano-graphene-carbon nanotube-ionic liquid composite membrane that preparation method obtains through the invention, integral thickness
It is to be overlapped mutually to be formed by multi-layer graphene lamella for 4000nm to 6000nm, the unordered of graphene in composite membrane can be reduced
Accumulation, improves the specific surface area of entire film.Nano-graphene-carbon nanotube-ionic liquid the composite membrane is in macroscopically paper-like knot
Structure, the microcosmic upper nano-lamellar structure in high-sequential；Nano-graphene-carbon nanotube-ionic liquid the composite membrane is by graphite
Alkene lamella is overlapped mutually to be formed, and the spacing between adjacent graphene sheet layer is 20nm~50nm, carbon nanotube and ionic liquid
It is dispersed between adjacent graphene sheet layer.The thickness of each graphene sheet layer can be several nanometers (that is, nano-graphite
Alkene lamella, such as 1nm~10nm), it can be connected with each other by pi bond by the graphene of multiple monoatomic layers and form (single an original
The thickness of the graphene of sublayer is about 0.335nm).
The present invention is by graphene oxide, carbon nanotube and ionic liquid (such as 1- butyl -3- methylimidazole tetrafluoro boric acids
Salt) three the sum of mixes and forms both graphene oxide and carbon nanotube concentration the graphite oxide for being 4mg/ml~6mg/ml
Alkene-carbon nanotube-ionic liquid mixed liquor, graphene oxide, carbon nanotube and ionic liquid three preferably press 1mg:(0.25mg
~0.5mg):The ratio of (5 μ l of μ l~10) is matched, it can be ensured that nano-graphene-carbon nanotube-ionic liquid of generation
Composite membrane is overlapped mutually by multi-layer graphene, the microcosmic upper nano-lamellar structure in high-sequential, by nano-graphene lamella
It is overlapped mutually to be formed, the spacing between adjacent nano-graphene lamella is 20nm~50nm, and carbon nanotube and ionic liquid are equal
It is even to be dispersed between the graphene nano lamella.The graphene oxide raw material that preparation method of the present invention uses is nanoscale oxygen
(size of graphene oxide is at several nanometers to hundreds of nanometers, it is preferred to use Hummers methods prepare graphene oxide for graphite alkene
Aqueous solution, then by obtaining graphene oxide after being freeze-dried the aqueous solution of the graphene oxide).
Preparation method provided by the present invention is simple to operate and friendly to environment, the composite film surface flat-satin of formation, machinery
Intensity is good, the large specific surface area of film, and electro-chemical activity is high.When laminated film provided by the invention is applied to nano electro-catalytic field
Heavy metal ion can be effectively detected, and detection limit is low, detection range is wide.In addition, by laminated film application provided by the invention
When field of biosensors is detected hydrogen peroxide small molecule, have higher detection sensitivity, application prospect very wide
It is wealthy.
Description of the drawings
Fig. 1 is the macrograph of graphene-carbon nano tube provided by the invention-ionic liquid composite membrane；
Fig. 2A and Fig. 2 B are profile scanning Electronic Speculum (SEM) figure of graphene-carbon nano tube-ionic liquid composite membrane, figure
2C and Fig. 2 D are flat scanning Electronic Speculum (SEM) figure of graphene-carbon nano tube-ionic liquid composite membrane；
Fig. 3 A, Fig. 3 B and Fig. 3 C are the x-ray photoelectron spectroscopies (XPS) of graphene-carbon nano tube-ionic liquid composite membrane
Figure, ordinate are photoelectron intensity, and abscissa is electron binding energy；Wherein, Fig. 3 A are graphene-carbon nano tube-ionic liquids
The full spectrogram of composite membrane, Fig. 3 B are that C1s spectrogram Fig. 3 C in graphene-carbon nano tube-ionic liquid composite membrane are graphenes-
N1s spectrograms in carbon nanotube-ionic liquid composite membrane；
Fig. 4 is the Raman energy spectrum figure of graphene-carbon nano tube-ionic liquid composite membrane prepared by embodiment 1, and ordinate is
Photoelectron relative intensity, abscissa are wave number；
Fig. 5 is graphene-carbon nano tube-ionic liquid laminated film of the preparation of embodiment 1 at HAc-NaAC (pH=4.6)
Using the ion concentration spectrogram of Pb and Cd in differential pulse voltammetry detection solution in buffer solution；
Fig. 6 is that graphene-carbon nano tube-ionic liquid laminated film prepared by embodiment 1 is buffered at PBS (pH=7.4)
To the cyclic voltammetric comparison diagram of the hydrogen peroxide of various concentration in solution.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
The preparation of 1 graphene oxide of embodiment
By 3g graphite powders, 3g sodium nitrate, 6g potassium permanganate and the 23ml concentrated sulfuric acids after mixing in normal-temperature water in ice bath
It is stirred to react 2h under bath.Temperature is risen to 35 DEG C, medium temperature reacts 3h.Continue at 90 DEG C after being gradually added into 100ml deionized waters
Stirring the reaction was continued 30min, mixture is by brown stain at glassy yellow.It is abundant using dilute hydrochloric acid solution and deionized water after cooling
Washing to filtrate is in pH=6.It is saved backup after graphene oxide filter cake is fully dried in 60 DEG C of vacuum drying ovens
The preparation of 2 graphene-carbon nano tubes of embodiment-ionic liquid laminated film
In the present embodiment 2, the preparation method of graphene-carbon nano tube-ionic liquid laminated film includes the following steps：
(1) it uses Hummers methods (such as embodiment 1) to prepare the aqueous solution of graphene oxide, is aoxidized after freeze-drying
Graphene powder.
(2) (milling time can be more than or equal to for grinding after being mixed graphene oxide, carbon nanotube and ionic liquid
Half an hour), graphene oxide quality：Carbon nanotube mass：The proportioning of ionic liquid volume three is 1mg:0.5mg:5 μ l, grind
Mixture after mill is dispersed in water, forms the oxidation that the sum of both graphene oxide and carbon nanotube concentration is 5mg/ml
Graphene-carbon nano tube-ionic liquid mixed liquor；
(3) graphene oxide-carbon nanotube-ionic liquid mixed liquor obtained in step (2) is taken into 150ml, with
Aperture is that the vacuum filtration instrument of the cellulose acetate class filter membrane of 220nm is separated by solid-liquid separation, the solid drying being separated by solid-liquid separation
Afterwards, graphene-carbon nano tube-ionic liquid film layer is detached with filter membrane can be obtained nano graphene oxide-carbon nanotube-ion
Liquid composite membrane；
(4) graphene oxide-carbon nanotube-ionic liquid composite membrane hydroiodic acid (hydroiodic acid that will be obtained in step (3)
Mass percentage concentration can be for example 45%) to restore, i.e. to obtain nano-graphene-carbon nanotube-ionic liquid multiple after reduction
Close film.
Nano-graphene-carbon nanotube-ionic liquid composite membrane is macroscopically solid film, ionic liquid and graphene, carbon
Very strong binding force is all had between nanotube so that the nano-graphene-carbon nanotube-ionic liquid composite membrane has good
Good entirety combination effect, can combine closely between nano-graphene and carbon nanotube.
3 graphene-carbon nano tubes of embodiment-ionic liquid laminated film detects heavy metal ion
Use graphene-carbon nano tube-ionic liquid laminated film for working electrode, reference electrode is saturation calomel electricity
Pole, auxiliary electrode are platinum electrode, are with 0.2mol/L acetate buffer solutions (pH=4.6, such as HAc-NaAc buffer solutions)
Test bottom liquid.Add 40mL 0.2mol/L HAc-NaAc buffer solutions (pH=4.6) in electrolytic cell, adds suitable Pb
(II) and Cd (II) standard solution it, is inserted into three-electrode system, set sedimentation potential as -1.2V, sedimentation time is 300s (stirring),
Stop stirring after preenrichment, static 10s is just being scanned using differential pulse voltammetry by negative sense, is measured and is recorded dissolution song
Line.Experiment is not necessarily to letting nitrogen in and deoxidizing, carries out at ambient temperature.By can be seen that in Fig. 5, the laminated film is dense in wider ion
Can be detected in degree range, and it is in a linear relationship between electric current and concentration, graphene-carbon nano tube-prepared by the present invention from
Sub- liquid laminated film substantially increases the detection limit of Pb and Cd ions, the graphene-carbon nano tube-ionic liquid laminated film
The minimum concentration of the Pb ions and Cd ions that can detect is respectively 0.2nmol/L and 0.1nmol/L.
4 graphene-carbon nano tubes of embodiment-ionic liquid laminated film is as no enzyme type hydrogen peroxide sensor
In three-electrode system, working electrode is graphene-carbon nano tube-ionic liquid laminated film, and auxiliary electrode is
Platinum electrode, reference electrode are saturated calomel electrode, and test bottom liquid is PBS (pH=7.4) buffer solution, and hydrogen peroxide is consequently formed
Without enzyme electrochemical sensor.As seen from Figure 6, with the increase of concentration of hydrogen peroxide, the electric current of cyclic voltammetry curve is gradual
Increase, shows preferable detection performance.
In above-described embodiment, carbon nanotube is carbon nanotube purchased in market, for example, the purity of carbon nanotube is preferably greater than 95%,
The diameter of carbon nanotube is preferably 10nm~20nm, and length is preferably 10 μm~30 μm；1- butyl -3- may be used in ionic liquid
Methyl imidazolium tetrafluoroborate ([bmim] BF4) ionic liquid, naturally it is also possible to use other ionic liquid at room temperature such as 1- butyl-
3- methylimidazole hexafluorophosphates.Graphene oxide powder is obtained after freeze-drying is generally nanoscale.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (7)
1. a kind of nano-graphene-carbon nanotube-ionic liquid composite membrane is in the application of detection heavy metal ion；
Nano-graphene-carbon nanotube-ionic liquid the composite membrane is using including that nano-graphene-carbon of following steps is received
What the preparation method of mitron-ionic liquid composite membrane was prepared：
(1) will graphene oxide, carbon nanotube and ionic liquid mix after be ground to obtain mixture, then, then this is mixed
It closes object to be dispersed in water, forms the graphite oxide that the sum of both graphene oxide and carbon nanotube concentration is 4mg/ml~6mg/ml
Alkene-carbon nanotube-ionic liquid mixed liquor；
(2) graphene oxide-carbon nanotube-ionic liquid mixed liquor that step described in 100ml~200ml (1) obtains is taken,
It is separated by solid-liquid separation by the vacuum filtration instrument with filter membrane, isolated solid is after drying and detaching with the filter membrane
Obtain nano graphene oxide-carbon nanotube-ionic liquid composite membrane；
(3) nano graphene oxide-carbon nanotube-ionic liquid composite membrane hydroiodic acid for obtaining the step (2)
Reduction obtains nano-graphene-carbon nanotube-ionic liquid composite membrane.
2. application as described in claim 1, the heavy metal ion is cadmium ion or lead ion.
3. a kind of nano-graphene-carbon nanotube-ionic liquid composite membrane is answered no enzyme type hydrogen peroxide electrochemical sensor
With；
Nano-graphene-carbon nanotube-ionic liquid the composite membrane is using including that nano-graphene-carbon of following steps is received
What the preparation method of mitron-ionic liquid composite membrane was prepared：
(1) will graphene oxide, carbon nanotube and ionic liquid mix after be ground to obtain mixture, then, then this is mixed
It closes object to be dispersed in water, forms the graphite oxide that the sum of both graphene oxide and carbon nanotube concentration is 4mg/ml~6mg/ml
Alkene-carbon nanotube-ionic liquid mixed liquor；
(2) graphene oxide-carbon nanotube-ionic liquid mixed liquor that step described in 100ml~200ml (1) obtains is taken,
It is separated by solid-liquid separation by the vacuum filtration instrument with filter membrane, isolated solid is after drying and detaching with the filter membrane
Obtain nano graphene oxide-carbon nanotube-ionic liquid composite membrane；
(3) nano graphene oxide-carbon nanotube-ionic liquid composite membrane hydroiodic acid for obtaining the step (2)
Reduction obtains nano-graphene-carbon nanotube-ionic liquid composite membrane.
4. being applied as described in claim 1-3 any one, which is characterized in that the graphene oxide in the step (1) is to adopt
The aqueous solution of graphene oxide is prepared with Hummers methods, then, is aoxidized after being freeze-dried the aqueous solution of the graphene oxide
Graphene.
5. being applied as described in claim 1-3 any one, which is characterized in that graphene oxide described in the step (1),
The carbon nanotube and the proportioning of the ionic liquid three are 1mg:(0.25mg~0.5mg):(5 μ l of μ l~10).
6. being applied as described in claim 1-3 any one, which is characterized in that the ionic liquid in the step (1) is 1- fourths
Base -3- methyl imidazolium tetrafluoroborates；The water in the step (1) is ultra-pure water.
7. being applied as described in claim 1-3 any one, which is characterized in that the graphite oxide in the step (1)
Alkene-carbon nanotube-ionic liquid mixed liquor also passes through ultrasonic disperse and handles.
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| CN107817287A (en) * | 2017-10-30 | 2018-03-20 | 上海应用技术大学 | A kind of sensor of detection nitrogen oxides based on nano graphene oxide and preparation method thereof |
| CN114232012B (en) * | 2021-09-29 | 2024-03-01 | 中国科学院金属研究所 | Ionic liquid modified nano carbon material catalyst and preparation method and application thereof |
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