CN106423154B - A kind of three-dimension flexible electrode or three-dimension flexible catalyst and their preparation and application - Google Patents
A kind of three-dimension flexible electrode or three-dimension flexible catalyst and their preparation and application Download PDFInfo
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- CN106423154B CN106423154B CN201610848339.6A CN201610848339A CN106423154B CN 106423154 B CN106423154 B CN 106423154B CN 201610848339 A CN201610848339 A CN 201610848339A CN 106423154 B CN106423154 B CN 106423154B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Abstract
The invention discloses a kind of three-dimension flexible electrode or three-dimension flexible catalyst and their preparation and application, wherein preparation method includes：(1) grown on carbon fibers zincite crystal array；(2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials；(3) preparation of carbon fiber/zinc oxide@poly-dopamines-noble metal composite-material.This method can also include step：(4) preparation of carbon fiber@nitrogen-doped carbons pipe-noble metal composite-material.The present invention is improved by the reaction condition etc. of integrated artistic design, each step to crucial preparation process, it can effectively solve the problem that the low problem of carbon fiber surface limited area, load nano material activity, carbon fiber obtained/zinc oxide@poly-dopamines-noble metal composite-material and carbon fiber@nitrogen-doped carbons pipe-noble metal composite-material are both three-dimension flexible electrode, it is also kind of a three-dimension flexible catalyst, catalytic effect is good, is particularly suitable for the detection to active oxygen radical in cancer cell.
Description
Technical field
The invention belongs to catalyst fields, and in particular, to a kind of three-dimension flexible electrode or three-dimension flexible catalyst and it
Preparation and application.
Background technology
Commodity are portable, under the market demand of microminiaturization, with the development and innovation of electronics industry, flexible micro-scale
Integrated electrochemical appliance makes electrochemical sensor that revolutionary variation have occurred.Such product has the ability to realize to chemistry in vivo
The real time monitoring of information and improve its stability.Carbon fiber electrode can not only meet electrode system in micron size range
Special requirement, special flexibility can also meet portable requirement.Specifically, carbon fiber illustrates one group of promising work(
Can, such as small size (5~30 microns of diameters), high intensity and springform, good biocompatibility, and low cost, this makes it
It can serve as in the electric signal conductive substrate of microelectrode.
Nowadays, primary carbon fibres are based on, reasonable design hierarchical structure can make the micro- of high-performance multifunctional nano hybrid
Electrode has more preferably development.However, the immobilization of the active material of carbon fiber surface, in the limited of carbon fiber-based on piece
Great challenge is encountered on surface area, this is because being supported on the low electroactive nano material of carbon fiber microelectrodes with micro pipette tips, is limited
The sensitivity for analysis of gained electrochemica biological sensor.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, it is an object of the invention to a kind of three-dimension flexible electrode and its
Preparation and application, wherein being designed by the integrated artistic to its crucial preparation process, (such as reactant is dense for the reaction condition of each step
Degree, reaction time, reaction temperature etc.) etc. be improved, can effectively solve the problem that carbon fiber surface area has compared with prior art
The low problem of limit, load nano material activity, the present invention are first to form zinc oxide array in carbon fiber surface, improve carbon fiber
Surface area, then poly-dopamine is coated on to the outside of zinc oxide, and noble metal granule is supported in poly-dopamine, it greatly improves
The load capacity of carbon fiber；Carbon fiber obtained/zinc oxide@poly-dopamines-noble metal composite-material and carbon fiber@N dopings
Carbon pipe-noble metal composite-material is both three-dimension flexible electrode, and kind three-dimension flexible catalyst, and catalytic effect is good, especially suitable
For the detection to active oxygen radical in cancer cell (i.e. ROS, such as hydrogen peroxide)；Due to the hydrophily of poly-dopamine, your gold
Belong to the surface that salt can also be uniformly adhered to poly-dopamine, more efficiently catalytic effect can be reached；Also, due to poly- DOPA
Carbon micron tube, the carbon nanotube that equivalent N doping is formd after amine carbonization, can further increase the three-dimension flexible catalyst (i.e.
Three-dimension flexible electrode) catalytic effect.
To achieve the above object, according to one aspect of the present invention, a kind of three-dimension flexible electrode or three-dimension flexible are provided
The preparation method of catalyst, which is characterized in that include the following steps：
(1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber after carbon fiber progress oxidation processes are aoxidized
Dimension；Then, the carbon fiber after the oxidation is immersed in the first mixed solution, crystalline growth aoxidizes at 250 DEG C~350 DEG C
Zinc seed, obtaining surface growth has the carbon fiber of zinc oxide seed, first mixed solution be using ethylene glycol monomethyl ether as solvent, it is molten
Matter includes zinc acetate and ethylenediamine；Then, the carbon fiber of zinc oxide seed is placed in the second mixed solution surface growth
In, hydro-thermal reaction is carried out at 90~110 DEG C, obtaining surface growth has the carbon fiber of zinc oxide, i.e. carbon fiber/zinc oxide compound
Material, second mixed solution are using water as solvent, and solute includes zinc nitrate and hexamethylenetetramine；
(2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane aqueous solution is prepared, it should
A concentration of 5mmol/L~10mmol/L of trishydroxymethylaminomethane in trishydroxymethylaminomethane aqueous solution；Then, according still further to
The charge ratios of 2mg~4mg Dopamine hydrochlorides is added per trishydroxymethylaminomethane aqueous solution described in 1mL to the trihydroxy methyl ammonia
Be added Dopamine hydrochloride in methylmethane aqueous solution, and be added into the trishydroxymethylaminomethane aqueous solution initiator make it is described
A concentration of 0.075mg/mL~0.1mg/mL of the initiator in the trishydroxymethylaminomethane aqueous solution；Then, 20 DEG C~
At a temperature of 40 DEG C, the carbon fiber/zinc oxide composite that the step (1) obtains is added to the trihydroxy methyl ammonia
In methylmethane aqueous solution, it is stirred to react at least 5h, Dopamine hydrochloride generation is made to polymerize and is wrapped in the carbon fiber/zinc oxide is multiple
On condensation material, the carbon fiber/zinc oxide composite coated by poly-dopamine, i.e. carbon fiber/poly- DOPA of zinc oxide@are obtained
Amine composite material；
(3) preparation of carbon fiber/zinc oxide@poly-dopamines-noble metal composite-material：Noble metal salt aqueous solution is prepared, it should
A concentration of 1mmol/L~10mmol/L of precious metal ion in noble metal salt aqueous solution；Then, by the noble metal salt aqueous solution
It is cooled down；Then, the carbon fiber/zinc oxide@poly-dopamine composite materials that the step (2) obtains are added to cooling
In the noble metal salt aqueous solution afterwards, it is stirred to react at a temperature of 0 DEG C~5 DEG C 10 minutes~30 minutes, is obtained after washing
Area load has the carbon fiber/zinc oxide@poly-dopamine composite materials of noble metal granule, i.e. carbon fiber/zinc oxide@poly- more
Bar amine-noble metal composite-material, the carbon fiber/zinc oxide@poly-dopamines-noble metal composite-material, that is, three-dimension flexible electrode or three
Tie up conformable catalyst.
It is another aspect of this invention to provide that providing the preparation side of a kind of three-dimension flexible electrode or three-dimension flexible catalyst
Method, which is characterized in that include the following steps：
(1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber after carbon fiber progress oxidation processes are aoxidized
Dimension；Then, the carbon fiber after the oxidation is immersed in the first mixed solution, crystalline growth aoxidizes at 250 DEG C~350 DEG C
Zinc seed, obtaining surface growth has the carbon fiber of zinc oxide seed, first mixed solution be using ethylene glycol monomethyl ether as solvent, it is molten
Matter includes zinc acetate and ethylenediamine；Then, the carbon fiber of zinc oxide seed is placed in the second mixed solution surface growth
In, hydro-thermal reaction is carried out at 90~110 DEG C, obtaining surface growth has the carbon fiber of zinc oxide, i.e. carbon fiber/zinc oxide compound
Material, second mixed solution are using water as solvent, and solute includes zinc nitrate and hexamethylenetetramine；
(2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane aqueous solution is prepared, it should
A concentration of 5mmol/L~10mmol/L of trishydroxymethylaminomethane in trishydroxymethylaminomethane aqueous solution；Then, according still further to
The charge ratios of 2mg~4mg Dopamine hydrochlorides is added per trishydroxymethylaminomethane aqueous solution described in 1mL to the trihydroxy methyl ammonia
Be added Dopamine hydrochloride in methylmethane aqueous solution, and be added into the trishydroxymethylaminomethane aqueous solution initiator make it is described
A concentration of 0.075mg/mL~0.1mg/mL of the initiator in the trishydroxymethylaminomethane aqueous solution；Then, 20 DEG C~
At a temperature of 40 DEG C, the carbon fiber/zinc oxide composite that the step (1) obtains is added to the trihydroxy methyl ammonia
In methylmethane aqueous solution, it is stirred to react at least 5h, Dopamine hydrochloride generation is made to polymerize and is wrapped in the carbon fiber/zinc oxide is multiple
On condensation material, the carbon fiber/zinc oxide composite coated by poly-dopamine, i.e. carbon fiber/poly- DOPA of zinc oxide@are obtained
Amine composite material；
(3) preparation of carbon fiber/zinc oxide@poly-dopamines-noble metal composite-material：Noble metal salt aqueous solution is prepared, it should
A concentration of 1mmol/L~10mmol/L of precious metal ion in noble metal salt aqueous solution；Then, by the noble metal salt aqueous solution
It is cooled down；Then, the carbon fiber/zinc oxide@poly-dopamine composite materials that the step (2) obtains are added to cooling
In the noble metal salt aqueous solution afterwards, it is stirred to react at a temperature of 0 DEG C~5 DEG C 10 minutes~30 minutes, is obtained after washing
Area load has the carbon fiber/zinc oxide@poly-dopamine composite materials of noble metal granule, i.e. carbon fiber/zinc oxide@poly- more
Bar amine-noble metal composite-material；
(4) preparation of carbon fiber@nitrogen-doped carbons pipe-noble metal composite-material：The carbon fiber that the step (3) is obtained
After dimension/zinc oxide@poly-dopamines-noble metal composite-material drying, carried out at carbonization in 500~700 DEG C in the environment of argon gas
Reason, it is the carbon pipe of N doping to make the poly-dopamine carbonization in the carbon fiber/zinc oxide@poly-dopamines-noble metal composite-material,
To obtain carbon fiber/zinc oxide@nitrogen-doped carbons pipe-noble metal composite-material；Then, the carbon fiber/zinc oxide@nitrogen is mixed
Miscellaneous carbon pipe-noble metal composite-material and acid solution reaction make the carbon fiber/zinc oxide@nitrogen-doped carbons pipe-noble metal composite-material
In zinc oxide dissolving, to obtain carbon fiber@nitrogen-doped carbons pipe-noble metal composite-material, carbon fiber@nitrogen-doped carbons pipe-
Noble metal composite-material, that is, three-dimension flexible electrode or three-dimension flexible catalyst.
As present invention further optimization, the initiator in the step (2) is cobalt chloride, cobalt nitrate, chlorination
At least one of copper, copper nitrate, nickel chloride and nickel nitrate；
In the step (3), the precious metal salt in the noble metal salt aqueous solution is potassium chloroaurate, potassium chloropalladate, chlorine Asia
At least one of palladium acid potassium, potassium chloroplatinate and silver nitrate.
As present invention further optimization, in the step (2), three hydroxyls in the trishydroxymethylaminomethane aqueous solution
The concentration of aminomethane is preferably 10mmol/L；In the step (3), precious metal ion in the noble metal salt aqueous solution
Concentration be preferably 5mmol/L.
It is described to be aoxidized carbon fiber progress oxidation processes in the step (1) as present invention further optimization
Carbon fiber afterwards is that carbon fiber is placed in the carbon fiber after 12h is aoxidized in hydrogen peroxide solution, is then washed with deionized water again
The carbon fiber after the oxidation is washed, then drying process obtains；Preferably, in the hydrogen peroxide solution hydrogen peroxide quality percentage
A concentration of 30%.
As present invention further optimization, in the step (1), zinc acetate is a concentration of in first mixed solution
0.01~0.03mol/L, a concentration of 0.01~0.03mol/L of ethylenediamine；Nitric acid zinc concentration in second mixed solution
For 0.08~0.2mol/L, a concentration of 0.08~0.2mol/L of hexamethylenetetramine；The duration of the hydro-thermal reaction is preferably
12 hours.
As present invention further optimization, in the step (3), the noble metal salt aqueous solution is cooled down, is
The noble metal salt aqueous solution is placed in ice bath and is cooled down.
As present invention further optimization, in the step (4), the carbon fiber/oxygen that the step (3) is obtained
Change zinc@poly-dopamines-noble metal composite-material drying, is by the carbon fiber/zinc oxide@poly-dopamines-noble metal composite wood
Material is freeze-dried；The carbonization treatment carries out in CVD stoves, the when a length of 2h of the carbonization treatment；By the carbon fiber
Dimension/zinc oxide@nitrogen-doped carbons pipe-noble metal composite-material and acid solution reaction are by the carbon fiber/zinc oxide@N dopings
Carbon pipe-noble metal composite-material is put into stirring 1h~5h in the acid solution, and the acid solution is hydrochloric acid solution, the hydrochloric acid solution
The concentration of middle hydrochloric acid is preferably 0.1mol/L.
Other side according to the invention provides the system using above-mentioned three-dimension flexible electrode or three-dimension flexible catalyst
The three-dimension flexible electrode or three-dimension flexible catalyst that Preparation Method is prepared.
Another aspect according to the invention provides the preparation using above-mentioned three-dimension flexible electrode or three-dimension flexible catalyst
Application of the three-dimension flexible electrode or three-dimension flexible catalyst that method is prepared in the hydrogen peroxide detection of cancer cell.
Contemplated above technical scheme through the invention, compared with prior art, due in carbon fiber surface growth of oxygen
Change the surface area that zinc crystal increases carbon fiber, and poly-dopamine is wrapped up on the surface of zincite crystal, nano-noble metal can be changed
The loadtype of catalyst solves the problems, such as that nano-metal particle is easy to reunite, improves the catalytic performance of catalyst, improve biology
The sensitivity for analysis of sensor.
Following advantageous effect can particularly be obtained：
1. the preparation method is that first (these zincite crystals are with zinc oxide to hydrothermal growth zincite crystal on carbon fiber
The form of crystal array is grown in carbon fiber surface), then wrapped up with poly-dopamine；With trishydroxymethylaminomethane tune when package
Saving solution ph, (that is, before polymerisation generates poly-dopamine, the pH value of the solution is preferably 7~8, three in corresponding solution
A concentration of 5mmol/L~10mmol/L of hydroxymethyl aminomethane), then using such as cobalt chloride etc. as initiator so that DOPA
The faster and better polymerization of amine energy.Then, the reproducibility of poly-dopamine is recycled noble metal is obtained by the reaction with precious metal salt solution
Nano particle, these noble metal nano particles are supported on the surface of carbon fiber/zinc oxide@poly-dopamine composite materials.Another party
Face is equivalent to after carbonization since poly-dopamine contains amino and is doped with nitrogen (corresponding to nitrogen-doped carbon pipe；Due to zinc oxide
Crystal array is also micro/nano level, and poly-dopamine is wrapped around the outer surface of each zincite crystal, therefore poly-dopamine
The nitrogen-doped carbon pipe formed after carbonization is also micro/nano level, i.e. nitrogen-doped carbon micron tube or nitrogen-doped carbon nanometer pipe), it is more advantageous to
Catalysis.The preparation method of the present invention, simple production process, raw material are easy to get, and mild condition is easy to operate, is easy to industrialize.Separately
Outside, the carbon fiber for having wrapped up poly-dopamine has good hydrophily, it is easier to the infiltration and infiltration of determinand aqueous solution, favorably
In the transmission of proton so that determinand is more effectively contacted with the gold nanoparticle for being carried on carbon fiber poly-dopamine surface, from
And reaction efficiency is greatly increased, enhance the sensitivity for analysis of electrochemical sensor.
2. the present invention is to reaction condition (such as reactant concentration, reaction time, the reaction temperature of each step in preparation process
Degree etc.) it optimizes so that poly-dopamine can be uniformly wrapped in above the zincite crystal of carbon fiber surface, in carbon
Fiber surface forms uniform, marshalling nitrogen-doped carbon pipe, substantially increases the surface area of carbon fiber；In addition, due to poly-
The hydrophily of dopamine, precious metal salt can also be uniformly adhered to the surface of poly-dopamine, be more efficiently catalyzed to reach
Effect.
To sum up, for the present invention using reaction material that is cheap, being easy to get, flexible 3 D structure catalyst obtained is (i.e. three-dimensional soft
Property electrode) it is easy to reuse.Moreover, this catalyst can be additionally used in the hydrogen peroxide detection of cancer cell, can quickly, accurately
Measurement cell (including normal cell and cancer cell) in hydrogen peroxide concentration, have high sensitivity, the strong feature of selectivity right
The application cost for reducing catalyst has good effect, can also realize the hydrogen peroxide concentration for monitoring cancer cell in real time in micron-scale
Variation.
Description of the drawings
Fig. 1 is carbon fiber@nitrogen-doped carbons pipe/gold of the present invention (that is, area load has gold nano grain and along carbon fiber
Surface distribution nitrogen-doped carbon pipe) preparation process schematic diagram；
Fig. 2A is carbon fiber/zinc oxide (that is, surface growth has the carbon fiber of zincite crystal, these zinc oxide brilliant in Fig. 2
Body is also micro-nano) scanning electron microscope (SEM) photograph；Fig. 2 B are carbon fiber/zinc oxide@poly-dopamines/gold (that is, being coated by poly-dopamine
Carbon fiber/zinc oxide, be also loaded gold nano grain on the outer surface of poly-dopamine) scanning electron microscope (SEM) photograph；Fig. 2 C are carbon
Fiber@nitrogen-doped carbons pipe/gold (that is, area load has the carbon pipe of gold nano grain, these carbon pipes are nitrogen-doping, and
These carbon pipes are also wrapped in the surface of carbon fiber) scanning electron microscope (SEM) photograph；Fig. 2 D are the transmission electricity of carbon fiber@nitrogen-doped carbons pipe/gold
Mirror figure；
Fig. 3 is that carbon fiber@nitrogen-doped carbons pipe/gold produced by the present invention is molten in the phosphoric acid buffer containing various concentration hydrogen peroxide
CV schemes in liquid, and the concentration of wherein hydrogen peroxide is respectively 0mM, 2mM, 4mM, 6mM and 8mM；
Fig. 4 is the I-T that hydrogen peroxide is added dropwise in carbon fiber@nitrogen-doped carbons pipe/gold produced by the present invention in phosphate buffer solution
Curve graph；
Fig. 5 A are the light field shows fluorescent microscopy images of cervical cancer cell in Fig. 5；Fig. 5 B are carbon fiber@nitrogen-doped carbons pipe/gold
I-T responses to hydrogen peroxide in cervical cancer cell.
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.
Embodiment 1
The synthesis of carbon fiber@nitrogen-doped carbons pipe/metal/composite material：
1) synthesis of carbon fiber/zinc oxide composite (that is, surface growth has the carbon fiber of zincite crystal)：By carbon fiber
Dimension be placed in 30% hydrogen peroxide (i.e. hydrogen peroxide mass percentage concentration for 30% aqueous hydrogen peroxide solution) in 12h aoxidized after carbon
Fiber, then drying is washed with deionized；Then the carbon fiber after above-mentioned oxidation is immersed in ethylene glycol monomethyl ether (No. CAS：
109-86-4) be solvent 0.01M zinc acetates and 0.01M ethylenediamine mixed solutions in, in Muffle furnace 300 DEG C of crystalline growths oxidation
Zinc seed (the zinc oxide kind crystalline substance is grown on carbon fiber)；Then the carbon fiber that grown zinc oxide seed is placed in simultaneously
Including in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions (solvent of the mixed solution can be water), obtain
To presoma；Then, presoma is placed in reaction kettle, and by reaction kettle be placed in 95 DEG C of baking oven carry out hydro-thermal reaction 12 it is small
When, obtain carbon fiber/zinc oxide composite；
2) carbon fiber/zinc oxide@poly-dopamines composite material is (that is, the carbon fiber/zinc oxide coated by poly-dopamine, gathers
Dopamine can especially be wrapped in the outside of zinc oxide) synthesis：Trishydroxymethylaminomethane is dissolved in deionized water and prepares 80mL
The aqueous solution of a concentration of 5mmol/L of trishydroxymethylaminomethane；Then, 160mg Dopamine hydrochlorides are added in this aqueous solution；It connects
The initiator cobalt chloride solution that a concentration of 6mg/mL of 1mL are added wherein；Finally carbon fiber/zinc oxide is hung at 20 DEG C
In above-mentioned solution, be stirred to react 20h, above-mentioned Dopamine hydrochloride made to occur to polymerize and be wrapped on carbon fiber, obtain carbon fiber/
Zinc oxide@poly-dopamine composite materials；
3) carbon fiber/zinc oxide@poly-dopamines/metal/composite material (that is, area load have the carbon fiber of gold nano grain/
Zinc oxide@poly-dopamines, gold nano grain can especially be supported on poly-dopamine surface) preparation：Gold potassium chloride is dissolved in water, is obtained
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto after this solution ice bath is pre-chilled to 5mM aqueous solution 50mL,
It is stirred to react 20min at 0 DEG C, the gold potassium chloride of surface attachment is then removed with the method for rinsing, then is freeze-dried, obtains
To carbon fiber/zinc oxide@poly-dopamines/metal/composite material；
4) carbon fiber@nitrogen-doped carbons pipe/metal/composite material (that is, area load has the carbon pipe of gold nano grain, these carbon pipes
Be nitrogen-doping, and these carbon pipes are also wrapped in the surface of carbon fiber) preparation：Above-mentioned carbon fiber/zinc oxide@is gathered
After dopamine/metal/composite material freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas, obtain carbon fiber/zinc oxide@nitrogen
Doped carbon pipe/metal/composite material (that is, area load has the carbon pipe of gold nano grain, these carbon pipes are nitrogen-doping, and
Zinc oxide is also enclosed in these carbon pipes, and along carbon fiber surface EDS maps)；Then the carbon fiber of gained/zinc oxide@nitrogen is mixed
Miscellaneous carbon pipe/metal/composite material, which is placed in the dilute hydrochloric acid of 0.1M, stirs 2h, obtain three-dimension flexible electrode carbon fiber nitrogen-doped carbon pipe/
Gold is (that is, area load has a gold nano grain and nitrogen-doped carbon pipe along carbon fiber surface EDS maps, these nitrogen-doped carbon pipes
Itself is also micro-nano, such as can be nitrogen-doped carbon nanometer pipe or nitrogen-doped carbon micron tube).The composite material can be used as
The detection of living cells hydrogen peroxide.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/metal/composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
Embodiment 2
The synthesis of carbon fiber@nitrogen-doped carbons pipe/palladium composite material：
1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber is placed in 12h in 30% hydrogen peroxide, uses deionized water
Wash drying；Then carbon fiber after above-mentioned oxidation is immersed in the 0.01M zinc acetates and 0.01M using ethylene glycol monomethyl ether as solvent
In ethylenediamine mixed solution, in 300 DEG C of crystalline growth zinc oxide seeds of Muffle furnace；Then the carbon fiber of zinc oxide seed will be grown
It includes to obtain presoma in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions that dimension, which is placed in,；Then, will before
It drives body to be placed in reaction kettle, and reaction kettle is placed on hydro-thermal reaction 12 hours in 95 DEG C of baking oven, it is multiple to obtain carbon fiber/zinc oxide
Condensation material；
2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane is dissolved in deionized water
Prepare the aqueous solution of a concentration of 8mmol/L of 80mL；Then, 160mg Dopamine hydrochlorides are added in this aqueous solution；Then wherein
The initiator cobalt chloride solution of a concentration of 6mg/mL of 1mL is added；Finally carbon fiber/zinc oxide is suspended at 20 DEG C above-mentioned molten
In liquid, it is stirred to react 20h, makes above-mentioned Dopamine hydrochloride occur to polymerize and be wrapped on carbon fiber, obtains carbon fiber/zinc oxide@
Poly-dopamine composite material；
3) preparation of carbon fiber/zinc oxide@poly-dopamines/palladium composite material：Palladium bichloride potassium is dissolved in water, obtains 5mM water
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto, after this solution ice bath is pre-chilled at 0 DEG C by solution 50mL
It is stirred to react 20min, the palladium bichloride potassium of surface attachment is then removed with the method for rinsing, then is freeze-dried, carbon fiber is obtained
Dimension/zinc oxide@poly-dopamines/palladium composite material；
4) preparation of the synthesis of carbon fiber@nitrogen-doped carbons pipe/palladium composite material：By above-mentioned carbon fiber/poly- DOPA of zinc oxide@
After amine/palladium composite material freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas；Then by carbon fiber/oxidation of gained
Zinc nitrogen-doped carbon pipe/palladium composite material is placed in the dilute hydrochloric acid of 0.1M and stirs 2h, obtains three-dimension flexible electrode carbon fiber nitrogen and mixes
Miscellaneous carbon pipe/palladium.The composite material can be used as the detection of living cells hydrogen peroxide content.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/palladium composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
Embodiment 3
The synthesis of carbon fiber@nitrogen-doped carbons pipe/metal/composite material：
1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber is placed in 12h in 30% hydrogen peroxide, uses deionized water
Wash drying；Then carbon fiber after above-mentioned oxidation is immersed in the 0.01M zinc acetates and 0.01M using ethylene glycol monomethyl ether as solvent
In ethylenediamine mixed solution, in 300 DEG C of crystalline growth zinc oxide seeds of Muffle furnace；Then the carbon fiber of zinc oxide seed will be grown
It includes to obtain presoma in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions that dimension, which is placed in,；Then, will before
It drives body to be placed in reaction kettle, and reaction kettle is placed on hydro-thermal reaction 12 hours in 95 DEG C of baking oven, it is multiple to obtain carbon fiber/zinc oxide
Condensation material；
2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane is dissolved in deionized water
Prepare the aqueous solution of a concentration of 8mmol/L of 80mL；Then, 160mg Dopamine hydrochlorides are added in this aqueous solution；Then wherein
The initiator copper nitrate solution of a concentration of 6mg/mL of 1mL is added；Finally carbon fiber/zinc oxide is suspended at 20 DEG C above-mentioned molten
In liquid, it is stirred to react 20h, makes above-mentioned Dopamine hydrochloride occur to polymerize and be wrapped on carbon fiber, obtains carbon fiber/zinc oxide@
Poly-dopamine composite material；
3) preparation of carbon fiber/zinc oxide@poly-dopamines/metal/composite material：Gold potassium chloride is dissolved in water, obtains 5mM water
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto, after this solution ice bath is pre-chilled at 0 DEG C by solution 50mL
It is stirred to react 20min, the gold potassium chloride of surface attachment is then removed with the method for rinsing, then is freeze-dried, carbon fiber is obtained
Dimension/zinc oxide@poly-dopamines/metal/composite material；
4) preparation of carbon fiber@nitrogen-doped carbons pipe/metal/composite material：By above-mentioned carbon fiber/zinc oxide@poly-dopamines/gold
After composite material freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas；Then by the carbon fiber of gained/zinc oxide@nitrogen
Doped carbon pipe/metal/composite material, which is placed in the dilute hydrochloric acid of 0.1M, stirs 2h, obtains three-dimension flexible electrode carbon fiber nitrogen-doped carbon
Pipe/gold.The composite material can be used as the detection of living cells hydrogen peroxide.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/metal/composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
Embodiment 4
The synthesis of carbon fiber@nitrogen-doped carbons pipe/metal/composite material：
1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber is placed in 12h in 30% hydrogen peroxide, uses deionized water
Wash drying；Then carbon fiber after above-mentioned oxidation is immersed in the 0.01M zinc acetates and 0.01M using ethylene glycol monomethyl ether as solvent
In ethylenediamine mixed solution, in 300 DEG C of crystalline growth zinc oxide seeds of Muffle furnace；Then the carbon fiber of zinc oxide seed will be grown
It includes to obtain presoma in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions that dimension, which is placed in,；Then, will before
It drives body to be placed in reaction kettle, and reaction kettle is placed on hydro-thermal reaction 12 hours in 95 DEG C of baking oven, it is multiple to obtain carbon fiber/zinc oxide
Condensation material；
2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane is dissolved in deionized water
Prepare the aqueous solution of a concentration of 5mmol/L of 80mL；Then, 240mg Dopamine hydrochlorides are added in this aqueous solution；Then wherein
The initiator cobalt chloride solution of a concentration of 6mg/mL of 1mL is added；Finally carbon fiber/zinc oxide is suspended at 20 DEG C above-mentioned molten
In liquid, it is stirred to react 20h, makes above-mentioned Dopamine hydrochloride occur to polymerize and be wrapped on carbon fiber, obtains carbon fiber/zinc oxide@
Poly-dopamine composite material；
3) preparation of carbon fiber/zinc oxide@poly-dopamines/metal/composite material：Gold potassium chloride is dissolved in water, obtains 5mM water
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto, after this solution ice bath is pre-chilled at 0 DEG C by solution 50mL
It is stirred to react 20min, the gold potassium chloride of surface attachment is then removed with the method for rinsing, then is freeze-dried, carbon fiber is obtained
Dimension/zinc oxide@poly-dopamines/metal/composite material；
4) preparation of carbon fiber@nitrogen-doped carbons pipe/gold：By above-mentioned carbon fiber/zinc oxide@poly-dopamines/metal/composite material
After freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas；Then by the carbon fiber of gained/zinc oxide@nitrogen-doped carbons pipe/
Metal/composite material is placed in the dilute hydrochloric acid of 0.1M and stirs 2h, obtains three-dimension flexible electrode carbon fiber nitrogen-doped carbon pipe/gold.This is multiple
Condensation material can be used as the detection of living cells hydrogen peroxide.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/metal/composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
Embodiment 4
The synthesis of carbon fiber@nitrogen-doped carbons pipe/metal/composite material：
1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber is placed in 12h in 30% hydrogen peroxide, uses deionized water
Wash drying；Then carbon fiber after above-mentioned oxidation is immersed in the 0.01M zinc acetates and 0.01M using ethylene glycol monomethyl ether as solvent
In ethylenediamine mixed solution, in 300 DEG C of crystalline growth zinc oxide seeds of Muffle furnace；Then the carbon fiber of zinc oxide seed will be grown
It includes to obtain presoma in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions that dimension, which is placed in,；Then, will before
It drives body to be placed in reaction kettle, and reaction kettle is placed on hydro-thermal reaction 12 hours in 95 DEG C of baking oven, it is multiple to obtain carbon fiber/zinc oxide
Condensation material；
2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane is dissolved in deionized water
Prepare the aqueous solution of a concentration of 10mmol/L of 80mL；Then, 240mg Dopamine hydrochlorides are added in this aqueous solution；Then at it
The middle initiator cobalt chloride solution that a concentration of 6mg/mL of 1mL are added；Finally carbon fiber/zinc oxide is suspended at 20 DEG C above-mentioned
In solution, it is stirred to react 20h, makes above-mentioned Dopamine hydrochloride occur to polymerize and be wrapped on carbon fiber, obtains carbon fiber/oxidation
Zinc@poly-dopamine composite materials；
3) preparation of carbon fiber/zinc oxide@poly-dopamines/metal/composite material：Gold potassium chloride is dissolved in water, obtains 5mM water
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto, after this solution ice bath is pre-chilled at 0 DEG C by solution 50mL
It is stirred to react 20min, the gold potassium chloride of surface attachment is then removed with the method for rinsing, then is freeze-dried, carbon fiber is obtained
Dimension/zinc oxide@poly-dopamines/metal/composite material；
4) preparation of carbon fiber@nitrogen-doped carbons pipe/gold：By above-mentioned carbon fiber/zinc oxide@poly-dopamines/metal/composite material
After freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas；Then by the carbon fiber of gained/zinc oxide@nitrogen-doped carbons pipe/
Metal/composite material is placed in the dilute hydrochloric acid of 0.1M and stirs 2h, obtain three-dimension flexible electrode carbon fiber/zinc oxide nitrogen-doped carbon pipe/
Gold.The composite material can be used as the detection of living cells hydrogen peroxide.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/metal/composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
Embodiment 5
The synthesis of carbon fiber@nitrogen-doped carbons pipe/metal/composite material：
1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber is placed in 12h in 30% hydrogen peroxide, uses deionized water
Wash drying；Then carbon fiber after above-mentioned oxidation is immersed in the 0.01M zinc acetates and 0.01M using ethylene glycol monomethyl ether as solvent
In ethylenediamine mixed solution, in 300 DEG C of crystalline growth zinc oxide seeds of Muffle furnace；Then the carbon fiber of zinc oxide seed will be grown
It includes to obtain presoma in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions that dimension, which is placed in,；Then, will before
It drives body to be placed in reaction kettle, and reaction kettle is placed on hydro-thermal reaction 12 hours in 95 DEG C of baking oven, it is multiple to obtain carbon fiber/zinc oxide
Condensation material；
2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane is dissolved in deionized water
Prepare the aqueous solution of a concentration of 5mmol/L of 80mL；Then, 160mg Dopamine hydrochlorides are added in this aqueous solution；Then wherein
The initiator cobalt chloride solution of a concentration of 6mg/mL of 1mL is added；Finally carbon fiber/zinc oxide is suspended at 20 DEG C above-mentioned molten
In liquid, it is stirred to react 20h, makes above-mentioned Dopamine hydrochloride occur to polymerize and be wrapped on carbon fiber, obtains carbon fiber/zinc oxide@
Poly-dopamine composite material；
3) preparation of carbon fiber/zinc oxide@poly-dopamines/metal/composite material：Gold potassium chloride is dissolved in water, obtains 10mM water
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto, after this solution ice bath is pre-chilled at 0 DEG C by solution 25mL
It is stirred to react 20min, the gold potassium chloride of surface attachment is then removed with the method for rinsing, then is freeze-dried, carbon fiber is obtained
Dimension/zinc oxide@poly-dopamines/metal/composite material；
4) preparation of carbon fiber@nitrogen-doped carbons pipe/gold：By above-mentioned carbon fiber/zinc oxide@poly-dopamines/metal/composite material
After freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas；Then by the carbon fiber of gained/zinc oxide@nitrogen-doped carbons pipe/
Metal/composite material is placed in the dilute hydrochloric acid of 0.1M and stirs 2h, obtains three-dimension flexible electrode carbon fiber nitrogen-doped carbon pipe/gold.This is multiple
Condensation material can be used as the detection of living cells hydrogen peroxide.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/metal/composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
Embodiment 6
The synthesis of carbon fiber@nitrogen-doped carbons pipe/silver composite material：
1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber is placed in 12h in 30% hydrogen peroxide, uses deionized water
Wash drying；Then carbon fiber after above-mentioned oxidation is immersed in the 0.01M zinc acetates and 0.01M using ethylene glycol monomethyl ether as solvent
In ethylenediamine mixed solution, in 300 DEG C of crystalline growth zinc oxide seeds of Muffle furnace；Then the carbon fiber of zinc oxide seed will be grown
It includes to obtain presoma in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions that dimension, which is placed in,；Then, will before
It drives body to be placed in reaction kettle, and reaction kettle is placed on hydro-thermal reaction 12 hours in 95 DEG C of baking oven, it is multiple to obtain carbon fiber/zinc oxide
Condensation material；
2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane is dissolved in deionized water
Prepare the aqueous solution of a concentration of 5mmol/L of 80mL；Then, 160mg Dopamine hydrochlorides are added in this aqueous solution；Then wherein
The initiator cobalt chloride solution of a concentration of 6mg/mL of 1mL is added；Finally carbon fiber/zinc oxide is suspended at 20 DEG C above-mentioned molten
In liquid, it is stirred to react 20h, makes above-mentioned Dopamine hydrochloride occur to polymerize and be wrapped on carbon fiber, obtains carbon fiber/zinc oxide@
Poly-dopamine composite material；
3) preparation of carbon fiber/zinc oxide@poly-dopamines/silver composite material：Silver nitrate is dissolved in water, it is water-soluble to obtain 10mM
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto, is stirred at 0 DEG C after this solution ice bath is pre-chilled by liquid 50mL
Reaction 20min is mixed, the silver nitrate of surface attachment is then removed with the method for rinsing, then is freeze-dried, carbon fiber/oxygen is obtained
Change zinc@poly-dopamines/silver composite material；
4) preparation of carbon fiber@nitrogen-doped carbons pipe/silver：By above-mentioned carbon fiber/zinc oxide@poly-dopamines/silver composite material
After freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas；Then by the carbon fiber of gained/zinc oxide@nitrogen-doped carbons pipe/
Silver composite material is placed in the dilute hydrochloric acid of 0.1M and stirs 2h, obtains three-dimension flexible electrode carbon fiber nitrogen-doped carbon pipe/silver.This is multiple
Condensation material can be used as the detection of living cells hydrogen peroxide.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/silver composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
Embodiment 7
The synthesis of carbon fiber@nitrogen-doped carbons pipe/silver composite material：
1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber is placed in 12h in 30% hydrogen peroxide, uses deionized water
Wash drying；Then carbon fiber after above-mentioned oxidation is immersed in the 0.01M zinc acetates and 0.01M using ethylene glycol monomethyl ether as solvent
In ethylenediamine mixed solution, in 300 DEG C of crystalline growth zinc oxide seeds of Muffle furnace；Then the carbon fiber of zinc oxide seed will be grown
It includes to obtain presoma in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions that dimension, which is placed in,；Then, will before
It drives body to be placed in reaction kettle, and reaction kettle is placed on hydro-thermal reaction 12 hours in 95 DEG C of baking oven, it is multiple to obtain carbon fiber/zinc oxide
Condensation material；
2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane is dissolved in deionized water
Prepare the aqueous solution of a concentration of 8mmol/L of 80mL；Then, 160mg Dopamine hydrochlorides are added in this aqueous solution；Then wherein
The initiator copper nitrate solution of a concentration of 10mg/mL of 1mL is added；Finally carbon fiber/zinc oxide is suspended at 20 DEG C above-mentioned
In solution, it is stirred to react 20h, makes above-mentioned Dopamine hydrochloride occur to polymerize and be wrapped on carbon fiber, obtains carbon fiber/oxidation
Zinc@poly-dopamine composite materials；
3) preparation of carbon fiber/zinc oxide@poly-dopamines/silver composite material：Silver nitrate is dissolved in water, it is water-soluble to obtain 10mM
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto, is stirred at 0 DEG C after this solution ice bath is pre-chilled by liquid 50mL
Reaction 20min is mixed, the silver nitrate of surface attachment is then removed with the method for rinsing, then is freeze-dried, carbon fiber/oxygen is obtained
Change zinc@poly-dopamines/silver composite material；
4) preparation of carbon fiber@nitrogen-doped carbons pipe/silver：By above-mentioned carbon fiber/zinc oxide@poly-dopamines/silver composite material
After freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas；Then by the carbon fiber of gained/zinc oxide@nitrogen-doped carbons pipe/
Silver composite material is placed in the dilute hydrochloric acid of 0.1M and stirs 2h, obtains three-dimension flexible electrode carbon fiber nitrogen-doped carbon pipe/silver.This is multiple
Condensation material can be used as the detection of living cells hydrogen peroxide.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/silver composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
Embodiment 8
The synthesis of carbon fiber/@nitrogen-doped carbons pipe/palladium composite material：
1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber is placed in 12h in 30% hydrogen peroxide, uses deionized water
Wash drying；Then carbon fiber after above-mentioned oxidation is immersed in the 0.01M zinc acetates and 0.01M using ethylene glycol monomethyl ether as solvent
In ethylenediamine mixed solution, in 300 DEG C of crystalline growth zinc oxide seeds of Muffle furnace；Then the carbon fiber of zinc oxide seed will be grown
Dimension is placed in comprising in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions, obtains presoma；Then, by forerunner
Body is placed in reaction kettle, and reaction kettle is placed on hydro-thermal reaction 12 hours in 95 DEG C of baking oven, and it is compound to obtain carbon fiber/zinc oxide
Material；
2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane is dissolved in deionized water
Prepare the aqueous solution of a concentration of 10mmol/L of 80mL；Then, 240mg Dopamine hydrochlorides are added in this aqueous solution；Then at it
The middle initiator copper nitrate solution that a concentration of 10mg/mL of 1mL are added；Finally carbon fiber/zinc oxide is suspended at 20 DEG C
It states in solution, is stirred to react 20h, make above-mentioned Dopamine hydrochloride occur to polymerize and be wrapped on carbon fiber, obtain carbon fiber/oxidation
Zinc@poly-dopamine composite materials；
3) preparation of carbon fiber/zinc oxide@poly-dopamines/palladium composite material：Palladium bichloride potassium is dissolved in water, obtains 10mM water
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto, after this solution ice bath is pre-chilled at 0 DEG C by solution 50mL
It is stirred to react 20min, the palladium bichloride potassium of surface attachment is then removed with the method for rinsing, then is freeze-dried, carbon fiber is obtained
Dimension/zinc oxide@poly-dopamines/palladium composite material；
4) preparation of carbon fiber/@nitrogen-doped carbons pipe/palladium：By above-mentioned carbon fiber/zinc oxide@poly-dopamines/palladium composite material
After freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas；Then by the carbon fiber of gained/zinc oxide@nitrogen-doped carbons pipe/
Palladium composite material is placed in the dilute hydrochloric acid of 0.1M and stirs 2h, obtains three-dimension flexible electrode carbon fiber/nitrogen-doped carbon pipe/palladium.This is multiple
Condensation material can be used as the detection of living cells hydrogen peroxide.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/palladium composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
Embodiment 9
The synthesis of carbon fiber/@nitrogen-doped carbons pipe/palladium composite material：
1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber is placed in 12h in 30% hydrogen peroxide, uses deionized water
Wash drying；Then carbon fiber after above-mentioned oxidation is immersed in the 0.01M zinc acetates and 0.01M using ethylene glycol monomethyl ether as solvent
In ethylenediamine mixed solution, in 300 DEG C of crystalline growth zinc oxide seeds of Muffle furnace；Then the carbon fiber of zinc oxide seed will be grown
Dimension is placed in comprising in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions, obtains presoma；Then, by forerunner
Body is placed in reaction kettle, and reaction kettle is placed on hydro-thermal reaction 12 hours in 95 DEG C of baking oven, and it is compound to obtain carbon fiber/zinc oxide
Material；
2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane is dissolved in deionized water
Prepare the aqueous solution of a concentration of 10mmol/L of 80mL；Then, 240mg Dopamine hydrochlorides are added in this aqueous solution；Then at it
The middle initiator nickel nitrate solution that a concentration of 6mg/mL of 1mL are added；Finally carbon fiber/zinc oxide is suspended at 20 DEG C above-mentioned
It in solution, is stirred to react for 24 hours, makes above-mentioned Dopamine hydrochloride occur to polymerize and be wrapped on carbon fiber, obtain carbon fiber/oxidation
Zinc@poly-dopamine composite materials；
3) preparation of carbon fiber/zinc oxide@poly-dopamines/palladium composite material：Palladium bichloride potassium is dissolved in water, obtains 5mM water
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto, after this solution ice bath is pre-chilled at 0 DEG C by solution 50mL
It is stirred to react 20min, the palladium bichloride potassium of surface attachment is then removed with the method for rinsing, then is freeze-dried, carbon fiber is obtained
Dimension/zinc oxide@poly-dopamines/palladium composite material；
4) preparation of carbon fiber/@nitrogen-doped carbons pipe/palladium：By above-mentioned carbon fiber/zinc oxide@poly-dopamines/palladium composite material
After freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas；Then by the carbon fiber of gained/zinc oxide@nitrogen-doped carbons pipe/
Palladium composite material is placed in the dilute hydrochloric acid of 0.1M and stirs 2h, obtains three-dimension flexible electrode carbon fiber/nitrogen-doped carbon pipe/palladium.This is multiple
Condensation material can be used as the detection of living cells hydrogen peroxide.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/palladium composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
Embodiment 10
The synthesis of carbon fiber@nitrogen-doped carbons pipe/silver composite material：
1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber is placed in 12h in 30% hydrogen peroxide, uses deionized water
Wash drying；Then carbon fiber after above-mentioned oxidation is immersed in the 0.01M zinc acetates and 0.01M using ethylene glycol monomethyl ether as solvent
In ethylenediamine mixed solution, in 300 DEG C of crystalline growth zinc oxide seeds of Muffle furnace；Then the carbon fiber of zinc oxide seed will be grown
Dimension is placed in comprising in 0.1M zinc nitrate hexahydrates and 0.1M hexamethylenetetramine mixed solutions, obtains presoma；Then, by forerunner
Body is placed in reaction kettle, and reaction kettle is placed on hydro-thermal reaction 12 hours in 95 DEG C of baking oven, and it is compound to obtain carbon fiber/zinc oxide
Material；
2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Trishydroxymethylaminomethane is dissolved in deionized water
Prepare the aqueous solution of a concentration of 10mmol/L of 80mL；Then, 320mg Dopamine hydrochlorides are added in this aqueous solution；Then at it
The middle initiator nickel nitrate solution that a concentration of 6mg/mL of 2mL are added；Finally carbon fiber/zinc oxide is suspended at 20 DEG C above-mentioned
In solution, it is stirred to react 20h, makes above-mentioned Dopamine hydrochloride occur to polymerize and be wrapped on carbon fiber, obtains carbon fiber/oxidation
Zinc@poly-dopamine composite materials；
3) preparation of carbon fiber/zinc oxide@poly-dopamines/silver composite material：Silver nitrate is dissolved in water, it is water-soluble to obtain 5mM
Carbon fiber/zinc oxide poly-dopamine composite material is added thereto, is stirred at 0 DEG C after this solution ice bath is pre-chilled by liquid 50mL
Reaction 20min is mixed, the silver nitrate of surface attachment is then removed with the method for rinsing, then is freeze-dried, carbon fiber/oxygen is obtained
Change zinc@poly-dopamines/silver composite material；
4) preparation of carbon fiber@nitrogen-doped carbons pipe/silver：By above-mentioned carbon fiber/zinc oxide@poly-dopamines/silver composite material
After freeze-drying, it is placed in CVD stoves and leads to 500 DEG C of carbonization 2h of argon gas；Then by the carbon fiber of gained/zinc oxide@nitrogen-doped carbons pipe/
Silver composite material is placed in the dilute hydrochloric acid of 0.1M and stirs 2h, obtains three-dimension flexible electrode carbon fiber nitrogen-doped carbon pipe/silver.This is multiple
Condensation material can be used as the detection of living cells hydrogen peroxide.
In addition, the carbon fiber obtained in the embodiment/zinc oxide@poly-dopamines/silver composite material intermediate product also can be straight
It connects as three-dimension flexible electrode or three-dimension flexible catalyst, is used for the detection of living cells hydrogen peroxide.
The preparation method of three-dimension flexible electrode in the present invention, simple for process, simple operation, environmental-friendly, reaction material
It is cheap and easy to get, the manufacturing cost of supported catalyst can be effectively reduced.
The amount of dopamine (i.e. Dopamine hydrochloride) can be adjusted according to actual demand, and amount volume is few to be can be achieved to carbon
The cladding ability of the zincite crystal grown on fiber, general is preferably 2~4mg/mL of mass concentration；Mole of precious metal salt
Amount can also be adjusted according to actual demand, the few catalysis that three-dimension flexible carbon fiber electrode can be achieved of amount volume.
The bound value and interval value of each raw material of the present invention can realize the present invention and cited initiator
Bound value and the area of the present invention and each technological parameter (such as temperature, reaction time) can be realized with precious metal salt
Between value can realize the present invention, embodiment is just not listed one by one herein.
Noble metal in the present invention is identical as the noble metal of traditional sense, i.e. gold, silver, palladium, platinum；In the present invention, carbon fiber
Oxidation other than using the hydrogen peroxide solution in above-described embodiment, the oxidation processes means of other carbon fibers can also be used, such as
Concentrated nitric acid, concentrated sulfuric acid etc., as long as can be in the surface graft functional group of carbon fiber.
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 (10)
1. the preparation method of a kind of three-dimension flexible electrode or three-dimension flexible catalyst, which is characterized in that include the following steps：
(1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber after carbon fiber progress oxidation processes are aoxidized；So
Afterwards, the carbon fiber after the oxidation is immersed in the first mixed solution, the crystalline growth zinc oxide kind at 250 DEG C~350 DEG C
Son, obtaining surface growth has the carbon fiber of zinc oxide seed, which is the solute packet using ethylene glycol monomethyl ether as solvent
Include zinc acetate and ethylenediamine；Then, the carbon fiber of zinc oxide seed is placed in the second mixed solution surface growth,
Hydro-thermal reaction is carried out at 90~110 DEG C, obtaining surface growth has the carbon fiber of zinc oxide, i.e. carbon fiber/zinc oxide composite,
Second mixed solution is using water as solvent, and solute includes zinc nitrate and hexamethylenetetramine；
(2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Prepare trishydroxymethylaminomethane aqueous solution, three hydroxyl
A concentration of 5mmol/L~10mmol/L of trishydroxymethylaminomethane in aminomethane aqueous solution；Then, according still further to every
The charge ratio of 2mg~4mg Dopamine hydrochlorides is added to the trihydroxy methyl amino in trishydroxymethylaminomethane aqueous solution described in 1mL
Dopamine hydrochloride is added in methane aqueous solution, and initiator is added into the trishydroxymethylaminomethane aqueous solution to make described draw
Send out a concentration of 0.075mg/mL~0.1mg/mL of the agent in the trishydroxymethylaminomethane aqueous solution；Then, 20 DEG C~40
At a temperature of DEG C, the carbon fiber/zinc oxide composite that the step (1) obtains is added to the trihydroxy methyl amino
In methane aqueous solution, it is stirred to react at least 5h, Dopamine hydrochloride generation is made to polymerize and is wrapped in the carbon fiber/zinc oxide is compound
On material, the carbon fiber/zinc oxide composite coated by poly-dopamine, i.e. carbon fiber/zinc oxide@poly-dopamines are obtained
Composite material；
(3) preparation of carbon fiber/zinc oxide@poly-dopamines-noble metal composite-material：Noble metal salt aqueous solution, your gold prepared
Belong to a concentration of 1mmol/L~10mmol/L of precious metal ion in saline solution；Then, the noble metal salt aqueous solution is carried out
It is cooling；Then, the carbon fiber/zinc oxide@poly-dopamine composite materials that the step (2) obtains are added to after cooling
In the noble metal salt aqueous solution, it is stirred to react at a temperature of 0 DEG C~5 DEG C 10 minutes~30 minutes, surface is obtained after washing
Load has the carbon fiber/zinc oxide@poly-dopamine composite materials of noble metal granule, i.e. carbon fiber/poly- DOPA of zinc oxide@
Amine-noble metal composite-material, the carbon fiber/zinc oxide@poly-dopamines-noble metal composite-material, that is, three-dimension flexible electrode or three-dimensional
Conformable catalyst.
2. the preparation method of a kind of three-dimension flexible electrode or three-dimension flexible catalyst, which is characterized in that include the following steps：
(1) synthesis of carbon fiber/zinc oxide composite：Carbon fiber after carbon fiber progress oxidation processes are aoxidized；So
Afterwards, the carbon fiber after the oxidation is immersed in the first mixed solution, the crystalline growth zinc oxide kind at 250 DEG C~350 DEG C
Son, obtaining surface growth has the carbon fiber of zinc oxide seed, which is the solute packet using ethylene glycol monomethyl ether as solvent
Include zinc acetate and ethylenediamine；Then, the carbon fiber of zinc oxide seed is placed in the second mixed solution surface growth,
Hydro-thermal reaction is carried out at 90~110 DEG C, obtaining surface growth has the carbon fiber of zinc oxide, i.e. carbon fiber/zinc oxide composite,
Second mixed solution is using water as solvent, and solute includes zinc nitrate and hexamethylenetetramine；
(2) synthesis of carbon fiber/zinc oxide@poly-dopamine composite materials：Prepare trishydroxymethylaminomethane aqueous solution, three hydroxyl
A concentration of 5mmol/L~10mmol/L of trishydroxymethylaminomethane in aminomethane aqueous solution；Then, according still further to every
The charge ratio of 2mg~4mg Dopamine hydrochlorides is added to the trihydroxy methyl amino in trishydroxymethylaminomethane aqueous solution described in 1mL
Dopamine hydrochloride is added in methane aqueous solution, and initiator is added into the trishydroxymethylaminomethane aqueous solution to make described draw
Send out a concentration of 0.075mg/mL~0.1mg/mL of the agent in the trishydroxymethylaminomethane aqueous solution；Then, 20 DEG C~40
At a temperature of DEG C, the carbon fiber/zinc oxide composite that the step (1) obtains is added to the trihydroxy methyl amino
In methane aqueous solution, it is stirred to react at least 5h, Dopamine hydrochloride generation is made to polymerize and is wrapped in the carbon fiber/zinc oxide is compound
On material, the carbon fiber/zinc oxide composite coated by poly-dopamine, i.e. carbon fiber/zinc oxide@poly-dopamines are obtained
Composite material；
(3) preparation of carbon fiber/zinc oxide@poly-dopamines-noble metal composite-material：Noble metal salt aqueous solution, your gold prepared
Belong to a concentration of 1mmol/L~10mmol/L of precious metal ion in saline solution；Then, the noble metal salt aqueous solution is carried out
It is cooling；Then, the carbon fiber/zinc oxide@poly-dopamine composite materials that the step (2) obtains are added to after cooling
In the noble metal salt aqueous solution, it is stirred to react at a temperature of 0 DEG C~5 DEG C 10 minutes~30 minutes, surface is obtained after washing
Load has the carbon fiber/zinc oxide@poly-dopamine composite materials of noble metal granule, i.e. carbon fiber/poly- DOPA of zinc oxide@
Amine-noble metal composite-material；
(4) preparation of carbon fiber@nitrogen-doped carbons pipe-noble metal composite-material：The carbon fiber that the step (3) is obtained/
After zinc oxide@poly-dopamines-noble metal composite-material drying, carbonization treatment is carried out in 500~700 DEG C in the environment of argon gas,
It is the carbon pipe of N doping to make the poly-dopamine carbonization in the carbon fiber/zinc oxide@poly-dopamines-noble metal composite-material, from
And obtain carbon fiber/zinc oxide@nitrogen-doped carbons pipe-noble metal composite-material；Then, by the carbon fiber/zinc oxide@N dopings
Carbon pipe-noble metal composite-material and acid solution reaction make in the carbon fiber/zinc oxide@nitrogen-doped carbons pipe-noble metal composite-material
Zinc oxide dissolving, to obtain carbon fiber@nitrogen-doped carbons pipe-noble metal composite-material, carbon fiber@nitrogen-doped carbons pipe-expensive
Metallic composite, that is, three-dimension flexible electrode or three-dimension flexible catalyst.
3. the preparation method of three-dimension flexible electrode as claimed in claim 1 or 2 or three-dimension flexible catalyst, which is characterized in that institute
It is at least one in cobalt chloride, cobalt nitrate, copper chloride, copper nitrate, nickel chloride and nickel nitrate to state the initiator in step (2)
Kind；
In the step (3), the precious metal salt in the noble metal salt aqueous solution is potassium chloroaurate, potassium chloropalladate, chlorine Asia palladium acid
At least one of potassium, potassium chloroplatinate and silver nitrate.
4. the preparation method of three-dimension flexible electrode as claimed in claim 1 or 2 or three-dimension flexible catalyst, which is characterized in that institute
It states in step (2), a concentration of 10mmol/L of trishydroxymethylaminomethane in the trishydroxymethylaminomethane aqueous solution；It is described
In step (3), a concentration of 5mmol/L of precious metal ion in the noble metal salt aqueous solution.
5. the preparation method of three-dimension flexible electrode as claimed in claim 1 or 2 or three-dimension flexible catalyst, which is characterized in that institute
State in step (1), it is described carbon fiber progress oxidation processes are aoxidized after carbon fiber, be that carbon fiber is placed in dioxygen is water-soluble
Carbon fiber after 12h is aoxidized in liquid is then washed with deionized the carbon fiber after the oxidation, is then dried again
It arrives；The mass percentage concentration of hydrogen peroxide is 30% in the hydrogen peroxide solution.
6. the preparation method of three-dimension flexible electrode as claimed in claim 1 or 2 or three-dimension flexible catalyst, which is characterized in that institute
State in step (1), a concentration of 0.01~0.03mol/L of zinc acetate in first mixed solution, ethylenediamine it is a concentration of
0.01~0.03mol/L；A concentration of 0.08~0.2mol/L of zinc nitrate in second mixed solution, hexamethylenetetramine
A concentration of 0.08~0.2mol/L；The hydro-thermal reaction when it is 12 hours a length of.
7. the preparation method of three-dimension flexible electrode as claimed in claim 1 or 2 or three-dimension flexible catalyst, which is characterized in that institute
It states in step (3), the noble metal salt aqueous solution is cooled down, be that the noble metal salt aqueous solution is placed in ice bath to carry out
It is cooling.
8. the preparation method of three-dimension flexible electrode as claimed in claim 1 or 2 or three-dimension flexible catalyst, which is characterized in that institute
It states in step (4), the carbon fiber that the step (3) is obtained/zinc oxide@poly-dopamines-noble metal composite-material drying,
It is to be freeze-dried the carbon fiber/zinc oxide@poly-dopamines-noble metal composite-material；The carbonization treatment is in CVD
It is carried out in stove, the when a length of 2h of the carbonization treatment；By the carbon fiber/zinc oxide@nitrogen-doped carbons pipe-noble metal composite-material
It is that the carbon fiber/zinc oxide@nitrogen-doped carbons pipe-noble metal composite-material is put into the acid solution with acid solution reaction
1h~5h is stirred, the acid solution is hydrochloric acid solution, a concentration of 0.1mol/L of hydrochloric acid in the hydrochloric acid solution.
9. utilizing the preparation method system of three-dimension flexible electrode or three-dimension flexible catalyst as described in claim 1-8 any one
Standby obtained three-dimension flexible electrode or three-dimension flexible catalyst.
10. utilizing the preparation method system of three-dimension flexible electrode or three-dimension flexible catalyst as described in claim 1-8 any one
The application of standby obtained three-dimension flexible electrode or three-dimension flexible catalyst in the active oxygen radical detection of cancer cell.
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| CN108212193B (en) * | 2018-01-25 | 2019-12-06 | 华中科技大学 | Preparation and application of fibrous catalyst loaded with metal nanoparticles |
| CN108273537B (en) * | 2018-01-25 | 2020-01-03 | 华中科技大学 | Preparation of metal nanoparticle-loaded nitrogen-doped graphite sieve tube |
| CN108831753B (en) * | 2018-06-20 | 2020-02-11 | 苏州大学 | Aramid fiber electrode and preparation method thereof |
| CN108878833B (en) * | 2018-06-27 | 2021-04-23 | 云南民族大学 | Carbon-coated LiNi0.10Mn1.90O4Positive electrode material and preparation method thereof |
| CN108906077A (en) * | 2018-07-02 | 2018-11-30 | 合肥萃励新材料科技有限公司 | A kind of zinc oxide synthetic method of Pd-Cu modification |
| CN110787827A (en) * | 2019-10-23 | 2020-02-14 | 华中科技大学 | Monoatomic catalyst, preparation method and application thereof |
| CN112255293B (en) * | 2020-10-15 | 2023-03-10 | 华中科技大学同济医学院附属协和医院 | Preparation method and application of microneedle electrode |
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