CN109748259A - A kind of preparation method and application of poly- polyphenol nanotube - Google Patents
A kind of preparation method and application of poly- polyphenol nanotube Download PDFInfo
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Abstract
The nanotube and purposes being prepared the present invention relates to a kind of preparation method of poly- polyphenol nanotube and by this method.The preparation method includes polyphenolic substance being carried out polymerization reaction in water-soluble template surface in organic solvent and in the presence of alkali, then the product that polymerization reaction is obtained is washed, and poly- polyphenol nanotube is obtained.The present invention is using water-soluble nano material as template, it is polymerize in organic solvent using polyphenolic substance, is successfully prepared the nano material of poly- polyphenol cladding, and removing template can be removed using simple water-washing method, poly- polyphenol nanotube is obtained, which forms carbon nanotube after carbonization.Obtained carbon nanotube has good hydrogen reduction performance, stability and methanol tolerance.
Description
Technical field
The invention belongs to field of material preparation, and in particular to a kind of preparation method of poly- polyphenol nanotube, by party's legal system
Standby poly- polyphenol nanotube and application thereof.
Background technique
Carbon nanotube is a kind of diameter in a few nanometers to tens of nanometers, length other monodimension nanometer material in the micron-scale,
By excellent electronic conductivity, high specific surface area, excellent thermomechanical property, unique optical property, in sensor, storage
The fields such as hydrogen material, capacitor, drug delivery, composite material, catalysis have a wide range of applications.
Polyphenol refers to the general designation of chemical element in a kind of plant, gains the name due to multiple phenolic hydroxyl groups.It is widely present in
In the plants such as tea, soybean, red wine, veterinary antibiotics, usually using phenyl ring as basic framework and containing great amount of hydroxy group, methoxyl group,
The characteristic groups such as methyl.Polyphenol has good antioxidant activity, can exist with other polyphenoils such as vitamin and carrotene
It plays anti-oxidation efficacy together in vivo, removes the free radical of harmful human health.It is made due to the unique structure feature of polyphenol
It is the hot spot of current domestic and foreign scholars research and concern with special physical property and chemical property.
Dopamine contains phenolic hydroxyl group and amino in structure as a kind of common polyphenolic substance.Under oxidative conditions,
Dopamine can form the poly-dopamine coating for being adhered tightly to the surface of solids.Since hydroxyl, amino etc. are contained in poly-dopamine surface
Active function groups, so having stronger adhesiveness.Also there are nontoxic, good biocompatibility, the spies such as biodegradable simultaneously
Point.Therefore, it is widely used in the fields such as surface modification, drug delivery, catalysis, lithium ion battery, water-oil separating.In addition, more
Bar amine can cause atom transfer radical polymerization (SIATRP) and surface self-initiating photografting polymerization (SIPGP) in base by surface
Bottom surface grafting functional polymer brush provides an ideal platform for the secondary modification of material.Therefore it is with dopamine
Precursor preparation nanotube, it will expand its applications in various fields.
In recent years, scientific research personnel polymerize dopamine in alkaline solution using zinc oxide nano rod as template, is formed poly- more
The zinc oxide nano rod ZnO PDA of bar amine cladding, finally removes removing template with HCl, is successfully prepared poly-dopamine nanotube.So
And this method washes away template with acid solution, removal condition is harsh, this may destroy the structure of poly-dopamine, also result in
Template removal is incomplete.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of method for preparing poly- polyphenol nanotube and is prepared by this method
Obtained poly- polyphenol nanotube.The pattern of the nanotube is uniformly, completely.
The present invention is achieved through the following technical solutions:
A kind of preparation method of poly- polyphenol nanotube, includes the following steps:
S1. polyphenolic substance carries out polymerization reaction in water-soluble template surface in organic solvent and in the presence of alkali；
S2. the product that step S1 polymerization reaction obtains is washed.
According to the method for the present invention, in step S1,
The polyphenolic substance can for levodopa (L-DOPA), dopamine (DA), norepinephrine, tannic acid,
One of tea polyphenols, catechol, two or more, preferably dopamine.
The polyphenolic substance can also be its derivative, for example, salt of polyphenolic substance or other groups modified compound
Object.
According to the present invention, the organic solvent is alcohols solvent, sulfone class solvent, amide solvent, one in ketones solvent
It plants, two or more.
For example, alcohols solvent can be selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, amylalcohol, decyl alcohol, n-dodecanol, ring
Amylalcohol, cyclohexanol, benzyl alcohol, benzyl carbinol；
Sulfone class solvent can be selected from dimethyl sulfoxide, dimethyl sulfone, sulfolane, 2,4- dimethylsulfolane；
Amide solvent can be selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide；
Ketones solvent is selected from acetone, methyl ethyl ketone.
The alkali can be selected from organic base or inorganic base, preferably organic base, such as ethylenediamine, triethylamine, butanediamine, three
One of butylamine, ring amine, two or more.
The water solubility template can be water-soluble nano material, such as sodium sulphate nano material, prodan nanometer material
Material；
The nano material can be nano wire, nanometer rods or nanotube；For example, sodium sulphate nano wire.
The quality of the polyphenolic substance and volume (g/L) ratio of alkali can be (100-300): 1, preferably (150-
250): 1, further preferably 200:1.
According to the method for the present invention, in step S2, further include the steps that being centrifuged product before washing and after washing.
Preferably, when polyphenolic substance polymerize in the presence of organic amine, with polyphenol Michael can occur for the organic amine
N in organic amine is introduced into poly- polyphenol nanotube by addition reaction.
The present invention also provides a kind of poly- polyphenol nanotubes prepared by the above method.
The present invention also provides the purposes of poly- polyphenol nanotube as described above, are used to prepare carbon nanotube.
The present invention also provides a kind of preparation methods of carbon nanotube, which comprises by the poly- polyphenol nanotube carbon
It is obtained after change.
According to the present invention, the carburizing temperature is 500-1000 DEG C, preferably 700-900 DEG C, for example, 850 DEG C.
According to the present invention, the carbonization time is 0.5-24 hours, for example, 3 hours.
According to the present invention, the heating rate of the carbonization is 1-10 DEG C/h, for example, 5 DEG C/h.
According to the present invention, the carbonization preferably carries out under atmosphere of inert gases, such as carries out in nitrogen.
The present invention also provides a kind of carbon nanotubes prepared by the above method.
The present invention also provides the purposes of carbon nanotube as described above, for the cathode reaction material for preparing fuel cell, especially
Ground is used as oxygen reduction catalyst.
Beneficial effect
Using water-soluble nano material, for example sodium sulphate nano wire is template to the present invention, using polyphenolic substance in organic solvent
Middle polymerization, is successfully prepared the nano material of poly- polyphenol cladding, and removes template using simple water-washing method, is prepared for poly- more
Phenol nanotube.This method is simple and convenient, can not only completely remove template, but also since removal mild condition (only uses water
Wash), the structure of poly- polyphenol will not be destroyed, to obtain pattern completely poly- polyphenol nanotube.Compared to traditional hard template method
The shortcomings that removal is difficult, and removal condition is harsh, and mantle plate method appearance and size is inhomogenous, bad dispersibility, water-soluble template, which has, easily goes
It removes, the advantages of favorable dispersibility.The poly- polyphenol nanotube has been obtained the complete carbon of pattern after carbonization and received by the present invention
Mitron.The carbon nanotube has biggish specific surface area and wide pore-size distribution (micropore, mesoporous, macropore have).Through electrochemistry
Test, the carbon nanotube have preferable hydrogen reduction performance, stability and methanol tolerance.
Detailed description of the invention
Figure 1A is Na2SO4The SEM picture of nano wire, B and C are respectively SEM and the TEM figure of poly-dopamine nanotube, and D is carbon
The TEM picture of nanotube.
Fig. 2 (A) is that (sweep speed is 50mv/ to CV curve of the DN-C in 0.1M KOH solution of the oxygen saturation with nitrogen saturation
s).(B) it is carbonized respectively at 650 DEG C, 750 DEG C and 850 DEG C obtained carbon nanotube and 20% business Pt/C for poly- polyphenol nanotube
The LSV curve graph of catalyst (sweeping speed is 10mv/s).It (C) is LSV curve of the DN-C catalyst under different rotating speeds.It (D) is DN-
The K-L line of C catalyst.(E) be DN-C and Pt/C catalyst chronoa mperometric plot (RDE revolving speed is 1600rpm, 0.15V).
It (F) is the methanol tolerance performance curve of DN-C catalyst.
Fig. 3 is the BET test result of DN-C.
Fig. 4 is the XPS characterization result of carbon nanotube DN-C-650, DN-C-750 and DN-C-850.
Specific embodiment
Further detailed description is done to technical solution of the present invention below in conjunction with specific embodiment.It should be appreciated that
The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.
In the range of all technologies realized based on above content of the present invention are encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
Preparation example 1Na2SO4The synthesis of nano wire:
Na2SO4The synthesis of nano wire uses method reported in the literature: it is accurate to measure 1.08g lauryl sodium sulfate,
It is molten to place it in 200ml DMF for 0.034g silver nitrate, 0.18g stannous chloride dihydrate, 0.146g cetyl trimethylammonium bromide
It in liquid, is heated to 160 DEG C and is flowed back with cooling circulating water, until mixed liquor becomes milky from colourless.Reaction product is centrifuged
(10000rpm, 5min) is cleaned three times repeatedly with ethyl alcohol, and final product is stored in spare in ethanol solution.
The synthesis of carbon nanotube derived from 1 poly-dopamine nanotube of embodiment and poly-dopamine
Measure 100ml Na2SO4Nano wire ethanol solution, ultrasonic disperse are uniform.200mg dopamine and tri- second of 1ml is added
Amine, mechanical stirring 48h.Product is centrifugated (10000rpm, 5min), and is cleaned repeatedly with water, centrifugation washes away sodium sulphate, obtains
To poly-dopamine nanotube.0.1g poly-dopamine nanotube is put into Noah's ark, is placed in tube furnace, under nitrogen atmosphere protection,
850 DEG C of carbonization 3h, 5 DEG C/min of heating rate finally obtain carbon nanotube derived from poly-dopamine and (are denoted as DN-C or DN-C-
850)。
Na used in the present embodiment2SO4The SEM and TEM of nano wire and the poly-dopamine nanotube being prepared, DN-C
Characterization result is as shown in Figure 1.
As shown in Figure 1, we are polymerize in ethanol using dopamine, for the first time using water-soluble sodium sulphate nano wire as template,
By simple water-washing method, it is successfully prepared poly-dopamine nanotube, which can prepare poly- DOPA by high temperature cabonization
Carbon nanotube derived from amine.
Also, as shown in Figure 1, poly-dopamine nanotube pattern prepared by the present invention is preferable, it maintains water after washing
Integrality before washing, surface were not destroyed.In addition, obtained carbon nanotube also has preferable pattern.
The DN-C-850 of preparation is subjected to N2Adsorption/desorption experiment, as a result as shown in figure 3, from the figure 3, it may be seen that DN-C-850
Specific surface area is up to 239.44m2/ g has preferable pore-size distribution in 0-100nm.
With reference to the preparation method of DN-C-850, poly-dopamine nanotube is carbonized at 650 DEG C and 750 DEG C respectively, is obtained
Carbon nanotube DN-C-650 and DN-C-750.XPS characterization result as shown in figure 4, be respectively DN-C-650, DN-C- from top to bottom
The characterization result of 750 and DN-C-850, as seen from Figure 4, the total nitrogen content of three kinds of carbon nanotubes respectively be up to 11.97%,
10.91 with 7.01%.
2 electrochemical property test of embodiment
The electrochemical property test of carbon nanotube (DN-C) prepared by embodiment 1 uses three-electrode system: glass-carbon electrode for
Working electrode, the platinum filament that diameter is 0.5mm are used as to electrode, and Ag/AgCl is as reference electrode.By 3mg catalyst (i.e. DN-C),
The Nafion solution of 30 μ l 5%, after being added to the mixing of 1ml dehydrated alcohol, ultrasonic disperse 30min.Then mixing drop-coated is covered
The disk electrode surface for being 3mm to diameter.Test electrolyte is 0.1M KOH solution.Oxygen or nitrogen are continually fed into before test
60min is to guarantee that electrolyte reaches saturation.The test scope of cyclic voltammetric is -0.8V-0.2V, sweep speed 50mv/s, line
Property scanning volt-ampere test scope be -0.8V-0.2V, sweep speed 10mv/s, test revolving speed be 400-2500rpm.Catalyst
Stability and methanol tolerance are tested using chronoamperometry.As a result as shown in Figure 2.
As shown in Figure 2, the DN-C catalyst that prepared by embodiment 1 has preferably starting electricity relative to commercialized 20%Pt/C
Position and limiting current density.Its electron transfer number is 4.2, is typical 4 electronics transfer.By chronoamperometry to catalyst
Stability is measured, which falls to the 89.4% of starting by 20000 seconds electric currents, and 20%Pt/C is reduced to originally
80.8%.After 5M methanol is added, which illustrates small change compared to 20%Pt/C, current density.Explanation
The catalyst has preferable stability and methanol tolerance performance.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of poly- polyphenol nanotube, which comprises the steps of:
S1. polyphenolic substance carries out polymerization reaction in water-soluble template surface in organic solvent and in the presence of alkali；
S2. the product that step S1 polymerization reaction obtains is washed.
2. the preparation method of poly- polyphenol nanotube as described in claim 1, which is characterized in that in step S1,
The polyphenolic substance is levodopa (L-DOPA), dopamine (DA), norepinephrine, tannic acid, tea polyphenols, youngster
One of tea phenol, two or more, preferably dopamine；
Preferably, the polyphenolic substance is its derivative, for example, salt of polyphenolic substance or other groups modified compound.
3. the preparation method of poly- polyphenol nanotube as claimed in claim 1 or 2, which is characterized in that in step S1,
The organic solvent be one of alcohols solvent, sulfone class solvent, amide solvent, ketones solvent, two or more；
Preferably, alcohols solvent can be selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, amylalcohol, decyl alcohol, n-dodecanol, ring penta
Alcohol, cyclohexanol, benzyl alcohol, benzyl carbinol；
Preferably, sulfone class solvent can be selected from dimethyl sulfoxide, dimethyl sulfone, sulfolane, 2,4- dimethylsulfolane；
Preferably, amide solvent can be selected from n,N-Dimethylformamide, n,N-dimethylacetamide；
Preferably, ketones solvent is selected from acetone, methyl ethyl ketone；
Preferably, the alkali is selected from organic base or inorganic base, also preferably organic base, for example, ethylenediamine, triethylamine, butanediamine,
One of tri-n-butylamine, ring amine, two or more.
4. the preparation method of poly- polyphenol nanotube as described in claim any one of 1-3, which is characterized in that described in step S1
Water-soluble template is water-soluble nano material, such as sodium sulphate nano material, prodan nano material；
Preferably, the nano material is nano wire, nanometer rods or nanotube；For example, sodium sulphate nano wire；
Preferably, the quality of the polyphenolic substance and the volume (g/L) of alkali are than being (100-300): 1, also preferably (150-
250): 1, further preferably 200:1.
5. the preparation method of poly- polyphenol nanotube as described in claim any one of 1-4, which is characterized in that in step S2, also wrap
The step of including before washing and product be centrifuged after washing.
6. a kind of poly- polyphenol nanotube being prepared by any one of claim 1-5 the method.
7. the purposes of poly- polyphenol nanotube as claimed in claim 6, which is characterized in that be used to prepare carbon nanotube.
8. a kind of preparation method of carbon nanotube, which is characterized in that the described method includes: by poly- polyphenol as claimed in claim 6
Nanotube is carbonized；
Preferably, the carburizing temperature is 500-1000 DEG C, preferably 700-900 DEG C, for example, 850 DEG C；
Preferably, the heating rate of the carbonization is 1-10 DEG C/h, for example, 5 DEG C/h；
Preferably, the carbonization carries out under atmosphere of inert gases, such as carries out in nitrogen.
9. the carbon nanotube being prepared by preparation method according to any one of claims 8.
10. the purposes of carbon nanotube as claimed in claim 9, which is characterized in that it is used to prepare fuel battery negative pole reaction wood
Material is particularly used as oxygen reduction catalyst.
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| CN115340804A (en) * | 2022-09-13 | 2022-11-15 | 福建刺桐花涂料科技有限公司 | Self-emulsifying formula for preparing water-based epoxy coating |
| WO2023155323A1 (en) * | 2022-02-17 | 2023-08-24 | 江阴纳力新材料科技有限公司 | Polyphenol-modified polymeric membrane, preparation method therefor and metallized polymeric membrane |
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