CN105353017B - A kind of double clicks of nickel cough up-carbon nanotube supermolecule composite material and its preparation and application - Google Patents
A kind of double clicks of nickel cough up-carbon nanotube supermolecule composite material and its preparation and application Download PDFInfo
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Abstract
- carbon nanotube supermolecule composite material and preparation method and application are coughed up the invention discloses a kind of double clicks of nickel.The double clicks of nickel of the invention cough up-and carbon nanotube supermolecule composite material is in UV-visible spectrum, it is coughed up relative to the double clicks of nickel, with in B, with red shift to 432nm and Q, two with red shift to 519nm weak absorption acromions have in Fourier transform-infrared spectrogram in 600-1800cm‑1The characteristic fingerprint that the double clicks of the nickel of range are coughed up.The double clicks of the nickel cough up-carbon nanotube supermolecule composite material for electrochemical biosensor decorative material, to detect electrocatalytic oxidation activity and selectivity to neurotransmitter dopamine.The preparation method is simple, conveniently, it is easily operated；There is high sensitivity, low detection limit, wide detection range to the detection of dopamine；The supramolecular complex of preparation also has high stability features as electrochemical sensing decorative material.
Description
Technical field
The invention belongs to materials science and engineering technical fields, and in particular to and a kind of double clicks of nickel cough up-and carbon nanotube is super
Molecular composite material (CNTs-NiNC) and its preparation method and application.
Background technique
Carbon nanotube (CNTs) has one-dimensional nano structure, is the carbon atom being in fragrant delocalization system by certain amount
The macromolecular of composition possesses high mechanical strength, the Field emission property that heat-flash leads ability, excellent.Porphyrin (porphyrin) is in porphin
The ring molecule for possessing the big pi-conjugated structure of one kind of substituent group on pheno (porphin) ring, has the planar structure and height of rigidity
Stabilization, big conjugated system make porphyrin have good electronics give ability.By the carbon nanotube with electron acceptability
Combine with porphyrin, realizes effective electron transmission between porphyrin and carbon nanotube, the nanocomposite system that can be constructed can
For fields such as bio-sensing, solar energy.Click cough up (corrole) and double click to cough up (norcorrole) be to be conjugated phases by 4 pyrroles
The novel porphyrin class macrocyclic complex (seeing below formula) even formed.Than porphyrin in middle position (meso) one or two few methylene respectively
Base has smaller cavity, can form stable complex with high-valence state metal after losing interior hydrogen atom.It not only has porphin
The similar property of quinoline also embodies some properties different from porphyrin, these characteristics cough up click in bioinorganic chemistry, catalysis
The fields such as chemistry, optical physics chemistry all have broad application prospects.It can be used as fine chemistry industry catalyst, fuel cell electrode is urged
Change material, anti-tumor photosensitizer, electrochemical sensor and nonlinear optical material.But starting is still in the research that click is coughed up at present
Stage, the research coughed up to double clicks are then less.
The porphyrin studied-carbon nanotube supramolecular system, mainly porphyrin in a manner of covalently or non-covalently pair
Carbon nanotube is modified.Non-covalent porphyrin-carbon nanotube systems preparation is relatively easy, and can keep to the maximum extent
The electronics of carbon nanotube and the integrality of structure.Currently, non-covalent fashion mainly includes pi-pi accumulation and model ylid bloom action, electrostatic
Attraction, coordination, polymer winding.But it so far, yet there are no any double clicks and cough up-the report of carbon nanotube supramolecular system
Road.Kobayashi and Shinokubo is prepared for after the double clicks of the nickel that can be stabilized cough up (NiNC), and only someone is using it as electrode
Active material is used for battery.
Summary of the invention
Present invention aims at non-covalent pi-pi accumulation principle is utilized, providing one kind, wet process prepares nickel in a mild condition
Double clicks cough up-simple scheme of carbon nanotube supermolecule composite material, and it is applied to electrochemical biosensor decorative material to detect
To the electrocatalytic oxidation activity and selectivity of neurotransmitter dopamine.
According to the first aspect of the invention, a kind of double clicks of nickel are provided and cough up-carbon nanotube supermolecule composite material, it is wrapped
It includes to cough up to be reacted or carried out to handle with carbon nanotube by the double clicks of nickel and is formed by supramolecular complex.
It is 1 that the double clicks of nickel, which are coughed up with the mass ratio of carbon nanotube (or molar ratio), in the composite:0.1-20, preferably 1:0.5-
10, more preferable 1:2-7.
Preferably, the reaction is pi-pi accumulation reaction or the processing is ultrasonic treatment.
Clicks double for a kind of above-mentioned nickel cough up-carbon nanotube supermolecule composite material, wherein in UV-visible spectrum,
It is coughed up relative to the double clicks of nickel, there is in B two with red shift to the 519nm weak absorption acromions with red shift to 432nm and Q, in Fourier
In leaf conversion-infrared spectrogram, have in 600-1800cm-1The characteristic fingerprint that the double clicks of the nickel of range are coughed up.
Further, above-mentioned nickel double clicks cough up-carbon nanotube supermolecule composite material is through the following steps that preparation：
(A) carbon nanotube is acidified；
(B) carbon nanotube of acidification and the double clicks of nickel are coughed up and is scattered in solvent, be ultrasonically treated, and be stirred to react (preferred
Be that the double clicks of nickel are coughed up has occurred pi-pi accumulation reaction between carbon nanotube)；
(C) mixture after reaction will be filtered, washed once or repeatedly；
(D) product after the washing of step (C) acquisition is dispersed in a solvent again, ultrasonic treatment, centrifuge separation removal of impurities takes
Clear liquid is dried after filtering coughs up-carbon nanotube supramolecular complex to get the double clicks of nickel.
Further, the double clicks of above-mentioned nickel cough up-carbon nanotube supermolecule composite material in, the double clicks of nickel are coughed up between carbon nanotube
Pi-pi accumulation reaction has occurred.
According to the second aspect of the invention, the double clicks of nickel are provided and cough up-preparation the side of carbon nanotube supermolecule composite material
Method the described method comprises the following steps：
(A) carbon nanotube is acidified；
(B) carbon nanotube of acidification and the double clicks of nickel are coughed up and is scattered in solvent, be ultrasonically treated, and be stirred to react (preferred
Be that the double clicks of nickel are coughed up has occurred pi-pi accumulation reaction between carbon nanotube)；
(C) mixture after reaction will be filtered, washed once or repeatedly (such as 2~10 times, preferably 3~6 times)；
(D) product after the washing of step (C) acquisition is dispersed in a solvent again, ultrasonic treatment, centrifuge separation removal of impurities takes
Clear liquid is dried after filtering coughs up-carbon nanotube supramolecular complex to get the double clicks of nickel.
Preferably, in step (A), be acidified used in acid be sulfuric acid, nitric acid, sulfuric acid and nitric acid nitration mixture it is (such as dense
HNO3(such as 68-69 mass %) and dense H2SO4(such as 70-98%) (V/V=1:3) nitration mixture).
Preferably, acid used in being acidified is nitration mixture (such as the dense HNO of sulfuric acid, nitric acid or sulfuric acid and nitric acid3(such as 68-
69 mass %) and dense H2SO4The nitration mixture of (such as 70-98%)；Such as two kinds of acid are according to volume ratio VNitric acid/VSulfuric acidIt is 1:1.3-5, it is excellent
It is selected as 1:1.8-4 such as 1:3 nitration mixture.
It is preferred that the acidification is included in dense HNO3With dense H2SO4(such as V/V=1:3) it in nitration mixture, is heated to reflux carbon and receives
Mitron 2-8 hours, preferably 3-5 hours, more preferably from about 4h were filtered with polytetrafluoroethylene (PTFE) miillpore filter (such as 0.22 μm of aperture),
It is washed repeatedly with deionized water repeatedly to neutral, 5 or more vacuum drying, such as 5-72 hours, preferably 20-30 hours, more preferably
About for 24 hours, acidification carbon nanotube is obtained.
Preferably, in the dissolution of step (B), the concentration of carbon nanotube in a solvent is 0.1-1.0mg/mL, preferably 0.5-
1.0mg/mL, it is 0.05~0.3mg/mL (saturated concentration), preferably 0.1~0.3mg/mL that the double clicks of nickel, which cough up concentration in a solvent,.
Preferably, step (B) is stirred to react 2~8 hours, preferably 3~5 hours, more preferably from about 3.5~4.5 at normal temperature
Hour.
Solvent used in step (B) and (D) is preferably polar organic solvent, e.g. one of amide or nitrile
Or a variety of, preferably one of formamide, acrylamide or acetonitrile or a variety of, more preferably n,N-Dimethylformamide
(DMF) it is used as solvent.
Ultrasonic treatment in step (B) and (D) can be 5 minutes~2 hours, preferably 10 minutes~30 minutes.
The length of acidification carbon nanotube in the application in step (A) is not particularly limited.
The third aspect of the invention provides the double clicks of above-mentioned nickel and coughs up-carbon nanotube supermolecule composite material or by above-mentioned
The double clicks of nickel of method preparation cough up-and carbon nanotube supermolecule composite material preparing the use in electrochemica biological sensor electrode
On the way.
In the present invention, multi-walled carbon nanotube is such as, but not limited to used：Nanjing Xian Feng Nono-material Science & Technology Ltd.,
Caliber：3-5 nanometers, pipe range:0.5-2 microns, purity：>95%.The synthesized reference that the double clicks of nickel are coughed up：Tomohiro Ito,Yosuke
Hayashi,Soji Shimizu,Ji-Young Shin,Nagao Kobayashi,and Hiroshi
Shinokubo.Gram-Scale Synthesis of Nickel(II)Norcorrole:The Smallest
Antiaromatic Porphyrinoid,Angew.Chem.2012,124,8670–8673。
Advantages of the present invention and effect
The double clicks of nickel provided by the invention cough up-and the preparation method of carbon nanotube supermolecule composite material is simple and convenient, is easy to grasp
Make.Resulting composite material so far there are no patent and document report.It is used to prepare using it as electrochemical sensing decorative material more
Bar amine electrochemica biological sensor electrode has selective electrocatalytic oxidation well, stability to neurotransmitter dopamine
It is good, it can be used for making dopamine electrochemica biological sensor.There is high sensitivity, low detection to limit the detection of dopamine,
Wide detection range；The supramolecular complex of preparation also has high stability features as electrochemical sensing decorative material.
Detailed description of the invention
The double clicks of the nickel of Fig. 1 embodiment of the present invention cough up (NiNC), carbon nanotube (CNTs) and the double clicks of nickel and cough up-carbon nanotube oversubscription
The UV-visible spectrum of sub- compound (CNTs-NiNC).
The double clicks of the nickel of Fig. 2 embodiment of the present invention cough up (NiNC), carbon nanotube (CNTs) and the double clicks of nickel and cough up-carbon nanotube oversubscription
Fourier transform-infrared spectrogram of sub- compound (CNTs-NiNC).
Fig. 3 A is the carbon nanotube of the embodiment of the present invention, and Fig. 3 B is that the double clicks of nickel cough up-carbon nanotube supramolecular complex (B)
Transmission electron microscope picture.
Fig. 4 A be the embodiment of the present invention preparation composite material as electrochemical sensing decorative material to neurotransmitter DOPA
The cyclic voltammogram of amine (DA) electrocatalytic oxidation, Fig. 4 B are the differential pulse voltammetry figure of selectivity with anti-interference test.
Specific embodiment
Here is that the double clicks of nickel of the present invention cough up the-specific embodiment of the preparation of carbon nanotube supermolecule composite material and application, with
Lower embodiment is further intended to that the present invention will be described in detail, is not intended to limit the present invention.
Embodiment
(1) processing of carbon nanotube：In dense HNO3With dense H2SO4(V/V=1:3) in nitration mixture, it is heated to reflux carbon nanotube
4h is filtered with 0.22 μm of aperture polytetrafluoroethylene (PTFE) miillpore filter, is washed repeatedly with deionized water repeatedly to neutral, vacuum drying
For 24 hours, gained acidification carbon nanotube remains to prepare composite material spare.
(2) the double clicks of nickel cough up the-preparation of carbon nanotube supermolecule composite material：Magneton is added in the single port bottle of 50mL, newly
The DMF 20mL of steaming, the double clicks of dissolution nickel cough up (NiNC) until saturation (about 0.3mg/mL), adds the carbon nanometer that 20mg is handled well
Pipe is ultrasonically treated 20min, and 4h is stirred to react under room temperature, is filtered after cooling with 0.22 μm of aperture polytetrafluoroethylene (PTFE) miillpore filter,
Washed repeatedly with DMF repeatedly colourless to filtrate, the double clicks of nickel to remove physical absorption are coughed up, and disperse obtained black solid in
It filters, washs 3 times after being ultrasonically treated in DMF；To remove unreacted CNTs, the product after washing is distributed in DMF ultrasonic
10min is centrifugated (repetitive operation is twice) under 4,500rmp revolving speed；Upper liquid is taken, with 0.22 μm of aperture polytetrafluoroethylene (PTFE)
Miillpore filter filters, and for 24 hours, gained atrament is that the double clicks of nickel cough up-carbon nanotube (mass ratio about 1 for vacuum drying:7) supermolecule is multiple
Close object, quality 9.3mg.
(3) the double clicks of nickel cough up the-characterization of carbon nanotube supermolecule composite material：It can be seen from figure 1 that the double clicks of nickel are coughed up in ultra-violet (UV) band
290nm has an absorption peak, it is seen that area has an absorption peak of B band in 428nm, one absorption peak 514nm of Q band, and there are also one at 474nm
Weak acromion；Two very weak suctions after being reacted with carbon nanotube, only in B with red shift to 432nm and Q with red shift to 519nm
Acromion is received, this property similar to porphyrin.Due to the strong electronic effect between big ring pi-electron and the pi-electron of carbon nano tube surface
So that the double clicks of nickel cough up the absorption decrease in visible light part, while red shift occurs.This tentatively illustrates that supramolecular complex is produced.
From Figure 2 it can be seen that in 600-1800cm-1Range, the double clicks of nickel cough up-and feature that the infrared spectroscopy of carbon nanotube is coughed up there are the double clicks of nickel refers to
Line.As seen from Figure 3, single carbon nanotube tube wall is very smooth (Fig. 3 A), rather than is covalently bonded with the single carbon that the double clicks of nickel are coughed up and receives
On mitron, it can be clearly seen that it is uneven on tube wall, it is connected to many small molecules (Fig. 3 B).This shows that the double clicks of nickel are coughed up
Pi-pi accumulation reaction has occurred between carbon nanotube, also further demonstrates that supermolecule composite material is successfully prepared.
(4) the double clicks of nickel cough up the-application of carbon nanotube supermolecule composite material
Test condition is as follows：The phosphate buffer solution of pH 6.8 is by NaH2PO4And NaH2PO4It prepares (PBS), experimental water
For secondary distilled water, 20ml glass detection cell, glass-carbon electrode of the three-electrode system containing modification is working electrode, platinum disk electrode is
Calomel electrode to electrode and saturation is reference electrode, and instrument is CHI760C type electrochemical workstation (Shanghai Chen Hua), is surveyed
Method for testing is cyclic voltammetry and differential pulse voltammetry, apply potential range be respectively -0.2~+0.7V and -0.35~+
0.6V。
The preparation of modified electrode：It pipettes the double clicks of 5 μ L nickel and coughs up-DMF the dispersion liquid of carbon nanotube, drop coating is in clean glass carbon electricity
The surface pole (GC), room temperature are dried.Then the electrode is placed in 0.1mol/L phosphate buffer (PBS), in -0.2~+0.8V
Potential range scan round is made the double clicks of nickel and coughs up-carbon nano tube modified glass-carbon electrode (CNTs-NiNC/ to electrode stable response
GC).For the electro catalytic activity for comparing composite material, the double clicks of nickel cough up the glass-carbon electrode (NiNC/GC) of modification with it is carbon nano tube modified
Glass-carbon electrode (CNTs/GC) by similar approach be made.
Electrocatalytic oxidation activity and the stability test method of composite material are as follows：In certain density neurotransmitter DOPA
In amine aqueous solution, it is inserted into three-electrode system, using cyclic voltammetry, cyclic voltammogram is obtained, utilizes the size of oxidation peak to peak current
Judge the power of catalysis oxidation dopamine.By Fig. 4 A as it can be seen that CNTs-NiNC has electrocatalytic oxidation more higher than CNTs and NiNC
Feature, the peak current of the former catalysis oxidation dopamine are respectively 1.86 times and 7.34 times of the latter.It is molten to the dopamine of same concentration
Liquid has carried out the scan round of 200 circles, and oxidation peak current is basically unchanged；Modified electrode after storage January is tested,
It will not reduce the electrocatalytic oxidation activity of dopamine, this proves that CNTs-NiNC is very stable.
Selectivity and disturbed test method are as follows：In certain density neurotransmitter dopamine (DA) solution, with CNTs-
NiNC/GC is working electrode, and conventional interference biomolecule ascorbic acid (AA) and uric acid (UA) is added, is lied prostrate using differential pulse
An Fa obtains the oxidation peak to peak current of DA, compares the variation of DA oxidation peak current before and after interfering substance is added.From fig. 4, it can be seen that
On CNTs-NiNC/GC, three kinds of biomolecule have selected different oxidizing potentials.By Fig. 4 B as it can be seen that being added before and after UA, the peak DA electricity
It flows substantially unchanged (homologous thread 1 and 2)；Equally, it in the system mixed at three kinds, is added before and after AA, DA peak current is also unchanged (right
Curve 3 and 4) is answered, illustrates that mixed UA and AA do not interfere the detection of DA.
Sample detection methods are as follows：The DA standard solution for pipetting various concentration sets detection cell, is inserted into three-electrode system, uses
Differential pulse voltammetry records oxidation peak current value under various concentration, draws standard curve.When detecting sample, the oxygen that will measure
Change peak point current and standard curve control, obtains the DA concentration of corresponding test sample.Testing result shows the detection to dopamine
With high sensitivity, low detection limit, wide detection range.
Claims (25)
1. a kind of double clicks of nickel cough up-carbon nanotube supermolecule composite material, it includes being coughed up to be reacted with carbon nanotube by the double clicks of nickel
Or it carries out processing and is formed by supramolecular complex；Wherein：
The carbon nanotube is acidified carbon nanotube；
It in the UV-visible spectrum of the material, coughs up, has in B band red shift to 432nm and Q band red shift relative to the double clicks of nickel
Have in Fourier transform-infrared spectrogram in 600-1800cm to two weak absorption acromions of 519nm-1The nickel of range
The characteristic fingerprint that double clicks are coughed up.
2. supermolecule composite material according to claim 1, wherein the reaction is pi-pi accumulation reaction or the processing is
Ultrasonic treatment.
3. the double clicks of nickel according to claim 1 or 2 cough up-carbon nanotube supermolecule composite material, through the following steps that
Preparation：
(A) carbon nanotube is acidified；
(B) carbon nanotube of acidification and the double clicks of nickel are coughed up and is scattered in solvent, be ultrasonically treated, and be stirred to react；
(C) mixture after reaction filtered, washed once or repeatedly；
(D) product after the washing of step (C) acquisition is dispersed in a solvent again, ultrasonic treatment, centrifuge separation removal of impurities takes clear liquid
It is dried after suction filtration and coughs up-carbon nanotube supramolecular complex to get the double clicks of nickel.
4. supermolecule composite material according to claim 3, it is characterised in that：Step (B) reaction is that the double clicks of nickel are coughed up
Pi-pi accumulation reaction has occurred between carbon nanotube.
5. the double clicks of nickel according to claim 1 cough up-and the preparation method of carbon nanotube supermolecule composite material, the method packet
Include following steps：
(A) carbon nanotube is acidified；
(B) carbon nanotube of acidification and the double clicks of nickel are coughed up and is scattered in solvent, be ultrasonically treated, and be stirred to react；
(C) mixture after reaction filtered, washed once or repeatedly；
(D) product after the washing of step (C) acquisition is dispersed in a solvent again, ultrasonic treatment, centrifuge separation removal of impurities takes clear liquid
It is dried after suction filtration and coughs up-carbon nanotube supramolecular complex to get the double clicks of nickel.
6. according to the method described in claim 5, it is characterized in that：Step (B) reaction coughs up for the double clicks of nickel and carbon nanotube
Between have occurred pi-pi accumulation reaction；Washing described in step (C) is washing 2~10 times.
7. method according to claim 5 or 6, wherein in step (A), being acidified used acid is sulfuric acid, nitric acid or sulphur
The nitration mixture of acid and nitric acid.
8. according to the method described in claim 7, wherein, the nitration mixture of the sulfuric acid and nitric acid is dense HNO3With dense H2SO4It is mixed
Acid；Two kinds of acid are according to volume ratio VNitric acid/VSulfuric acidIt is 1:1.3-5.
9. according to the method described in claim 8, wherein, the nitric acid is 68-69 mass %, and the sulfuric acid is 70-98%, two
Kind acid is according to volume ratio VNitric acid/VSulfuric acidIt is 1:1.8-4.
10. the method according to any one of claim 5,6,8 or 9, wherein in the dissolution of step (B), carbon nanotube exists
Concentration in solvent is 0.1-1.0mg/mL, and it is 0.05~0.3mg/mL that the double clicks of nickel, which cough up concentration in a solvent,；And/or
Wherein, it is stirred to react 2~8 hours at normal temperature or under heating in step (B).
11. according to the method described in claim 7, wherein, in the dissolution of step (B), the concentration of carbon nanotube in a solvent is
0.1-1.0mg/mL, it is 0.05~0.3mg/mL that the double clicks of nickel, which cough up concentration in a solvent,；And/or
Wherein, it is stirred to react 2~8 hours at normal temperature or under heating in step (B).
12. according to the method described in claim 10, wherein, the concentration of carbon nanotube in a solvent is 0.5-1.0mg/mL, nickel
It is 0.1~0.3mg/mL that double clicks, which cough up concentration in a solvent,；And/or
Wherein, it is stirred to react 3~5 hours at normal temperature or under heating in step (B).
13. according to the method for claim 11, wherein the concentration of carbon nanotube in a solvent is 0.5-1.0mg/mL, nickel
It is 0.1~0.3mg/mL that double clicks, which cough up concentration in a solvent,；And/or
Wherein, it is stirred to react 3~5 hours at normal temperature or under heating in step (B).
14. the method according to any one of 5,6,8,9 or 11-13 of claim, wherein used in step (B) or (D)
Solvent be one of amide or nitrile or a variety of.
15. according to the method described in claim 7, wherein, solvent used in step (B) or (D) is in amide or nitrile
It is one or more.
16. according to the method described in claim 10, wherein, solvent used in step (B) or (D) is in amide or nitrile
It is one or more.
17. according to the method for claim 14, wherein solvent used in step (B) or (D) is formamide, propylene
One of amide or acetonitrile are a variety of.
18. according to the method for claim 15, wherein solvent used in step (B) or (D) is formamide, propylene
One of amide or acetonitrile are a variety of.
19. according to the method for claim 16, wherein solvent used in step (B) or (D) is formamide, propylene
One of amide or acetonitrile are a variety of.
20. method described in any one of 7-19 according to claim 1, wherein solvent used in step (B) or (D) is
N,N-dimethylformamide is as solvent.
21. the method according to any one of claim 5,6,8,9,11-13 or 15-19, wherein in step (B) and (D)
Sonication treatment time be 5 minutes~2 hours.
22. according to the method described in claim 7, wherein, the sonication treatment time in step (B) and (D) is 5 minutes~2 small
When.
23. according to the method described in claim 10, wherein, the sonication treatment time in step (B) and (D) is 5 minutes~2 small
When.
24. according to the method for claim 21, wherein the sonication treatment time in step (B) and (D) is 10 minutes~30
Minute.
25. the double clicks of nickel of any of claims 1-4 cough up-carbon nanotube supermolecule composite material or pass through claim
The double clicks of nickel of the preparation of method described in any one of 5-24 cough up-and carbon nanotube supermolecule composite material passes preparing electrochemica biological
Purposes in sensor electrode.
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