CN103558273B - A kind of preparation method of zinc oxide nanowire array/foamy graphene composite material - Google Patents
A kind of preparation method of zinc oxide nanowire array/foamy graphene composite material Download PDFInfo
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Abstract
The preparation method of zinc oxide nanowire array/foamy graphene composite material and an application thereof, relate to a kind of preparation method and application thereof of compound substance.The present invention will solve current material to be applied to the technical matters that when L-3,4 dihydroxyphenylalanine detects, sensitivity is low and detectability is higher.Preparation method of the present invention is as follows: one, chemical vapour deposition technique; Two, hydrothermal synthesis method.A kind of zinc oxide nanowire array/foamy graphene composite material can detect L-3,4 dihydroxyphenylalanine as electrode material.The present invention is mainly for the preparation of a kind of zinc oxide nanowire array/foamy graphene composite material.
Description
Technical field
The present invention relates to a kind of preparation method of compound substance
Background technology
The Two-dimensional Carbon nano material of the tightly packed cellular structure of hexangle type that Graphene is made up of with sp2 hybrid orbital monolayer carbon atom.The special monatomic structure of Graphene makes it have the performance of good heat conduction and a series of excellence such as electric conductivity, high specific surface area, preferably chemical stability, become one of material that research is the hottest at present, paid close attention to widely, application prospect is boundless.The preparation method of current Graphene is a lot, and wherein applying is carry out micromechanics stripping, chemical oxidization method and chemical vapour deposition technique to graphite more widely.Graphite peeled off by micromechanics can prepare high-quality Graphene, but productive rate is lower, is not suitable for large-scale production.Chemical oxidization method is subject to the favor of many researchists because the low and output of cost is large, but the Graphene inside that this method is produced is containing a large amount of defect, the a large amount of chemical group of lamella margin residual, makes its electric conductivity greatly reduce, limits the application of Graphene to a certain extent.Graphene prepared by chemical vapour deposition technique is subject to the consistent accreditation of researchist and Graphene manufacturer with its superior electrical property; This wherein utilizes nickel foam to have few defect, high electrical conductance as foamy graphite alkene prepared by template auxiliary chemical vapor deposition method, have large voidage and three-dimensional network appearance simultaneously, provide good platform for combining with metal oxide nano-material, but the hydrophobic nature of Graphene proposes a lot of challenge to this material and metal oxide combination.
Zinc paste is a kind of important wide bandgap semiconductor materials, room-temperature exciton binding energy 60meV, superpower electron mobility.Zinc paste, owing to having good biocompatibility, electrochemical stability, high electro-catalysis efficiency, is therefore considered to a kind of sensitive material with very high researching value, has potential using value in electrochemica biological sensor field.Zinc oxide nanowire can provide directly, electron channel and specific surface area are large fast, but its relatively poor electrical conductance hinders its application to a certain extent.The preparation method of zinc oxide nano-wire array has metal organic vapor to grow usually, chemical vapor deposition, physical vapour deposition (PVD), the methods such as Hydrothermal Synthesis.Wherein to have synthesis temperature low for hydrothermal synthesis method, with low cost and can large-scale production, therefore receives much concern.
Parkinson's are a kind of common nervous system degeneration diseases, and its clinical manifestation mainly comprises static tremor, bradykinesia, myotonia and posture gait disorder, and patient can with non-motor symptoms such as depression, constipation and sleep-disorder simultaneously.The topmost pathological change of Parkinson's is that the sex change of substantia nigra of midbrain dopaminergic neuron is dead, causes Striatal Dopamine Content conspicuousness reduce and cause a disease therefrom.L-3,4 dihydroxyphenylalanine is the source being widely used in treatment Parkinson disease dopamine, and L-3,4 dihydroxyphenylalanine can generate dopamine, to make up the deficiency of brain dopamine by blood cerebral disorders under the effect of AADC.L-3,4 dihydroxyphenylalanine preparation is still the most effective medicine for the treatment of Parkinson's at present, but long-term taking L-3,4 dihydroxyphenylalanine but can produce toxic and side effect.Therefore, accurately determine that the content of L-3,4 dihydroxyphenylalanine in human body has very important significance.Current report be applied to L-3,4 dihydroxyphenylalanine detect sensitivity lower, be generally less than 1 μ A/ μm ol/L and detectability taller and bigger in 75nmol/L.
Summary of the invention
The present invention will solve current material to be applied to the technical matters that when L-3,4 dihydroxyphenylalanine detects, sensitivity is low and detectability is higher, thus provides a kind of preparation method of zinc oxide nanowire array/foamy graphene composite material.
The preparation method of a kind of zinc oxide nanowire array/foamy graphene composite material of the present invention carries out according to the following steps:
One, chemical vapour deposition technique:
1) nickel foam is placed in quartz tube furnace central authorities, under the protection of argon gas and hydrogen, be heated to temperature from room temperature with the 20 DEG C/min ~ 40 DEG C/heating rate of min is 1000 DEG C ~ 1100 DEG C, and be incubated 30min ~ 60min under the condition of 1000 DEG C ~ 1100 DEG C in temperature, be in tubular furnace, pass into methane gas 5min ~ 20min with the speed of 5sccm ~ 10sccm under the condition of 1000 DEG C ~ 1100 DEG C in temperature, then quartz tube furnace is 1000 DEG C ~ 1100 DEG C from temperature is cooled to room temperature with the 80 DEG C/min ~ 100 DEG C/cooldown rate of min, obtain the nickel foam of being wrapped up by Graphene, step one 1) described in nickel foam density be 420g/m
2~ 440g/m
2, thickness is 1.6mm ~ 2.0mm, step one 1) described in the flow velocity of argon gas be 480sccm ~ 500sccm, the flow velocity of hydrogen is 180sccm ~ 200sccm,
2) polymethylmethacrylate is dissolved in ethyl lactate, and be add thermal agitation 1h ~ 2h under the condition of 80 DEG C ~ 120 DEG C to obtain mixed solution in temperature, the use amount of 100 μ L ~ 200 μ L is had to utilize sample loading gun that mixed solution is added drop-wise to step one 1 by every square centimeter) nickel foam of being wrapped up by Graphene that obtains is on the surface, then at room temperature natural drying is be incubated the foamy graphite alkene that 0.5h ~ 1h obtains Surface coating polymethylmethacrylate under the condition of 150 DEG C ~ 200 DEG C in temperature; Step one 2) described in mixed solution in the massfraction of methyl methacrylate be 4% ~ 5%;
3) by step one 2) to cut into surface area be 0.5cm for the foamy graphite alkene of Surface coating polymethylmethacrylate that obtains
2~ 2cm
2cube, and be soaked in that temperature is 80 DEG C ~ 90 DEG C completely, concentration is the three-dimensional foam Graphene that in the hydrochloric acid solution of 3mol/L ~ 4mol/L, 4h ~ 6h obtains removing nickel;
4) by step one 3) to be soaked in temperature be 0.5h ~ 1.5h in the acetone of 60 DEG C ~ 70 DEG C for the three-dimensional foam Graphene of removal nickel that obtains, obtain the foamy graphite alkene removing polymethylmethacrylate, then with distilled water, the foamy graphite alkene removing polymethylmethacrylate is cleaned up, then the foamy graphite alkene of the removal polymethylmethacrylate cleaned up is transferred on clean ito glass, the use amount of 50 μ L ~ 100 μ L is had to utilize sample loading gun to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up by zinc oxide seed layer solution by every square centimeter again, being placed in temperature is again be incubated 20min ~ 30min under the condition of 150 DEG C ~ 200 DEG C, obtain the three-dimensional foam Graphene/ito glass being prefabricated with zinc oxide seed layer, step one 4) described in clean ito glass be ito glass successively ultrasonic cleaning 15min ~ 20min in acetone successively, ultrasonic cleaning 15min ~ 20min and deionized water for ultrasonic cleaning 15min ~ 20min in ethanol, at room temperature natural drying obtains, step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methyl alcohol, then with the rotating speed magnetic agitation 3min ~ 5min of 450r/min ~ 550r/min, obtain zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.001mol/L ~ 0.05mol/L,
Two, hydrothermal synthesis method:
1) zinc nitrate and hexamethylene tetramine are dissolved in deionized water, obtain hydro-thermal reaction solution with the rotating speed magnetic agitation 3min ~ 5min of 450r/min ~ 550r/min; Step 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.05mol/L ~ 0.1mol/L; The concentration of hexamethylene tetramine is 0.05mol/L ~ 0.1mol/L;
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) during the three-dimensional foam Graphene being prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in reactor mixed solution, cover reactor lid, 6h ~ 12h is reacted under the temperature conditions of 90 DEG C ~ 110 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain compound substance, open reactor distilled water compound substance is cleaned up, and 1h ~ 1.5h is incubated at 400 DEG C ~ 450 DEG C, cool to room temperature with the furnace, namely zinc oxide nanowire array/foamy graphene composite material is obtained.
An application for zinc oxide nanowire array/foamy graphene composite material, zinc oxide nanowire array/foamy graphene composite material uses as working electrode.
Advantage of the present invention:
(1) the inventive method prepares the flawless three-dimensional foam Graphene of high conductance by chemical vapor deposition, Bound moisture thermal synthesis is at the zinc oxide nano-wire array of graphenic surface vertical-growth high-specific surface area simultaneously, has prepared the zinc oxide nano-wire array/three-dimensional foam graphene composite material of new structure;
(2) compound substance of the present invention can play the synergy of high conductance Graphene and high-specific surface area zinc oxide nano-wire array, zinc oxide nano-wire array utilizes Seed Layer to prepare the combination that can improve zinc paste and Graphene, and the existence of zinc oxide nano-wire array, countless active sites is provided at graphenic surface, and the electron transmission that reaction can directly produce by zinc oxide nanowire is on Graphene, realize the fast transfer of electronics, therefore electrocatalysis characteristic can be significantly improved, the sensitivity of Electrochemical Detection L-3,4 dihydroxyphenylalanine can be made to improve significantly to 2.2 μ A/ μm ol/L, and make the detectability of L-3,4 dihydroxyphenylalanine be reduced to 50nmol/L.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the amplification 200 times of zinc oxide nanowire array/foamy graphene composite material prepared by test one;
Fig. 2 is the stereoscan photograph of the amplification 500 times of zinc oxide nanowire array/foamy graphene composite material prepared by test one;
Fig. 3 is the stereoscan photograph of the amplification 2000 times of zinc oxide nanowire array/foamy graphene composite material prepared by test one;
Fig. 4 is the stereoscan photograph of the amplification 10000 times of zinc oxide nanowire array/foamy graphene composite material prepared by test one;
Fig. 5 is the stereoscan photograph of the amplification 50000 times of zinc oxide nanowire array/foamy graphene composite material prepared by test one;
Fig. 6 is X ray diffracting spectrum, curve a is test one step one 4) in the X ray diffracting spectrum of the foamy graphite alkene of removal polymethylmethacrylate that cleans up, ● the diffraction peak of Graphene, curve b is the X ray diffracting spectrum of zinc oxide nanowire array/foamy graphene composite material prepared by test one, ● the diffraction peak of Graphene, ▲ be the diffraction peak of zinc paste;
Fig. 7 is test one step one 4) in the specific surface area curve of the foamy graphite alkene of removal polymethylmethacrylate that cleans up, curve a is adsorption curve, and curve b is desorption curve;
Fig. 8 is the specific surface area curve of zinc oxide nanowire array/foamy graphene composite material prepared by test one, and curve a is adsorption curve, and curve b is desorption curve;
Fig. 9 is the Linear Fit Chart of the L-3,4 dihydroxyphenylalanine concentration that obtains of test two and electric current.
Embodiment
Embodiment one: in present embodiment, a kind of preparation method of zinc oxide nanowire array/foamy graphene composite material carries out according to the following steps:
One, chemical vapour deposition technique:
1) nickel foam is placed in quartz tube furnace central authorities, under the protection of argon gas and hydrogen, be heated to temperature from room temperature with the 20 DEG C/min ~ 40 DEG C/heating rate of min is 1000 DEG C ~ 1100 DEG C, and be incubated 30min ~ 60min under the condition of 1000 DEG C ~ 1100 DEG C in temperature, be in tubular furnace, pass into methane gas 5min ~ 20min with the speed of 5sccm ~ 10sccm under the condition of 1000 DEG C ~ 1100 DEG C in temperature, then quartz tube furnace is 1000 DEG C ~ 1100 DEG C from temperature is cooled to room temperature with the 80 DEG C/min ~ 100 DEG C/cooldown rate of min, obtain the nickel foam of being wrapped up by Graphene, step one 1) described in nickel foam density be 420g/m
2~ 440g/m
2, thickness is 1.6mm ~ 2.0mm, step one 1) described in the flow velocity of argon gas be 480sccm ~ 500sccm, the flow velocity of hydrogen is 180sccm ~ 200sccm,
2) polymethylmethacrylate is dissolved in ethyl lactate, and be add thermal agitation 1h ~ 2h under the condition of 80 DEG C ~ 120 DEG C to obtain mixed solution in temperature, the use amount of 100 μ L ~ 200 μ L is had to utilize sample loading gun that mixed solution is added drop-wise to step one 1 by every square centimeter) nickel foam of being wrapped up by Graphene that obtains is on the surface, then at room temperature natural drying is be incubated the foamy graphite alkene that 0.5h ~ 1h obtains Surface coating polymethylmethacrylate under the condition of 150 DEG C ~ 200 DEG C in temperature; Step one 2) described in mixed solution in the massfraction of methyl methacrylate be 4% ~ 5%;
3) by step one 2) to cut into surface area be 0.5cm for the foamy graphite alkene of Surface coating polymethylmethacrylate that obtains
2~ 2cm
2cube, and be soaked in that temperature is 80 DEG C ~ 90 DEG C completely, concentration is the three-dimensional foam Graphene that in the hydrochloric acid solution of 3mol/L ~ 4mol/L, 4h ~ 6h obtains removing nickel;
4) by step one 3) to be soaked in temperature be 0.5h ~ 1.5h in the acetone of 60 DEG C ~ 70 DEG C for the three-dimensional foam Graphene of removal nickel that obtains, obtain the foamy graphite alkene removing polymethylmethacrylate, then with distilled water, the foamy graphite alkene removing polymethylmethacrylate is cleaned up, then the foamy graphite alkene of the removal polymethylmethacrylate cleaned up is transferred on clean ito glass, the use amount of 50 μ L ~ 100 μ L is had to utilize sample loading gun to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up by zinc oxide seed layer solution by every square centimeter again, being placed in temperature is again be incubated 20min ~ 30min under the condition of 150 DEG C ~ 200 DEG C, obtain the three-dimensional foam Graphene/ito glass being prefabricated with zinc oxide seed layer, step one 4) described in clean ito glass be ito glass successively ultrasonic cleaning 15min ~ 20min in acetone successively, ultrasonic cleaning 15min ~ 20min and deionized water for ultrasonic cleaning 15min ~ 20min in ethanol, at room temperature natural drying obtains, step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methyl alcohol, then with the rotating speed magnetic agitation 3min ~ 5min of 450r/min ~ 550r/min, obtain zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.001mol/L ~ 0.05mol/L,
Two, hydrothermal synthesis method:
1) zinc nitrate and hexamethylene tetramine are dissolved in deionized water, obtain hydro-thermal reaction solution with the rotating speed magnetic agitation 3min ~ 5min of 450r/min ~ 550r/min; Step 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.05mol/L ~ 0.1mol/L; The concentration of hexamethylene tetramine is 0.05mol/L ~ 0.1mol/L;
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) during the three-dimensional foam Graphene being prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in reactor mixed solution, cover reactor lid, 6h ~ 12h is reacted under the temperature conditions of 90 DEG C ~ 110 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain compound substance, open reactor distilled water compound substance is cleaned up, and 1h ~ 1.5h is incubated at 400 DEG C ~ 450 DEG C, cool to room temperature with the furnace, namely zinc oxide nanowire array/foamy graphene composite material is obtained.
The advantage of present embodiment:
(1) the inventive method prepares the flawless three-dimensional foam Graphene of high conductance by chemical vapor deposition, the zinc oxide nano-wire array that Bound moisture thermal synthesis is simultaneously tied at graphenic surface vertical-growth high-ratio surface, has prepared the zinc oxide nano-wire array/three-dimensional foam graphene composite material of new structure;
(2) compound substance of the present invention can play the synergy of high conductance Graphene and high-specific surface area zinc oxide nano-wire array, zinc oxide nano-wire array utilizes Seed Layer to prepare the combination that can improve zinc paste and Graphene, and the existence of zinc oxide nano-wire array, countless active sites is provided at graphenic surface, and the electron transmission that reaction can directly produce by zinc oxide nanowire is on Graphene, realize the fast transfer of electronics, therefore electrocatalysis characteristic can be significantly improved, the sensitivity of Electrochemical Detection L-3,4 dihydroxyphenylalanine can be made to improve significantly to 2.2 μ A/ μm ol/L, and make the detectability of L-3,4 dihydroxyphenylalanine be reduced to 50nmol/L.
Embodiment two: present embodiment and embodiment one are unlike step one 1) in nickel foam is placed in quartz tube furnace central authorities, under the protection of argon gas and hydrogen, be heated to temperature from room temperature with the 25 DEG C/min ~ 35 DEG C/heating rate of min is 1000 DEG C ~ 1100 DEG C, and be incubated 40min ~ 50min under the condition of 1000 DEG C ~ 1100 DEG C in temperature, be in tubular furnace, pass into methane gas 10min ~ 15min with the speed of 7sccm ~ 9sccm under the condition of 1000 DEG C ~ 1100 DEG C in temperature, then quartz tube furnace is 1000 DEG C ~ 1100 DEG C from temperature is cooled to room temperature with the 85 DEG C/min ~ 95 DEG C/cooldown rate of min, obtain the nickel foam of being wrapped up by Graphene, step one 1) described in nickel foam density be 425g/m
2~ 435g/m
2, thickness is 1.6mm ~ 2.0mm, step one 1) described in the flow velocity of argon gas be 500sccm, the flow velocity of hydrogen is 200sccm.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two are unlike step one 2) in polymethylmethacrylate is dissolved in ethyl lactate, and be add thermal agitation 1h ~ 2h under the condition of 90 DEG C ~ 110 DEG C to obtain mixed solution in temperature, the use amount of 130 μ L ~ 170 μ L is had to utilize sample loading gun that mixed solution is added drop-wise to step one 1 by every square centimeter) nickel foam of being wrapped up by Graphene that obtains is on the surface, at room temperature natural drying, then be incubated the foamy graphite alkene that 0.5h ~ 1h obtains Surface coating polymethylmethacrylate under the condition of 150 DEG C ~ 200 DEG C in temperature, step one 2) described in mixed solution in the massfraction of methyl methacrylate be 4% ~ 5%.Other is identical with one of embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are unlike step one 3) in by step one 2) to cut into surface area be 1.0cm for the foamy graphite alkene of Surface coating polymethylmethacrylate that obtains
2~ 1.5cm
2cube, and be soaked in that temperature is 80 DEG C ~ 90 DEG C completely, concentration is the three-dimensional foam Graphene that in the hydrochloric acid solution of 3mol/L ~ 4mol/L, 4.5h ~ 5.5h obtains removing nickel.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four are unlike step one 4) in by step one 3) to be soaked in temperature be 0.5h ~ 1.5h in the acetone of 60 DEG C ~ 70 DEG C for the three-dimensional foam Graphene of removal nickel that obtains, obtain the foamy graphite alkene removing polymethylmethacrylate, then with distilled water, the foamy graphite alkene removing polymethylmethacrylate is cleaned up, then the foamy graphite alkene of the removal polymethylmethacrylate cleaned up is transferred on clean ito glass, the use amount of 70 μ L ~ 90 μ L is had to utilize sample loading gun to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up by zinc oxide seed layer solution by every square centimeter again, being placed in temperature is again be incubated 20min ~ 30min under the condition of 170 DEG C ~ 190 DEG C, obtain the three-dimensional foam Graphene/ito glass being prefabricated with zinc oxide seed layer, step one 4) described in clean ito glass be ito glass successively ultrasonic cleaning 15min ~ 20min in acetone successively, ultrasonic cleaning 15min ~ 20min and deionized water for ultrasonic cleaning 15min ~ 20min in ethanol, at room temperature natural drying obtains, step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methyl alcohol, then with the rotating speed magnetic agitation 3min ~ 5min of 450r/min ~ 550r/min, obtain zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.005mol/L ~ 0.01mol/L.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five are unlike step 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.06mol/L ~ 0.08mol/L; The concentration of hexamethylene tetramine is 0.06mol/L ~ 0.08mol/L.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are unlike step 2 2) in by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) during the three-dimensional foam Graphene being prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in reactor mixed solution, cover reactor lid, 8h ~ 10h is reacted under the temperature conditions of 90 DEG C ~ 110 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain compound substance, open reactor distilled water compound substance is cleaned up, and 1h ~ 1.5h is incubated at 420 DEG C ~ 440 DEG C, cool to room temperature with the furnace, namely zinc oxide nanowire array/foamy graphene composite material is obtained.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is a kind of application of zinc oxide nanowire array/foamy graphene composite material, and zinc oxide nanowire array/foamy graphene composite material uses as working electrode.
Present embodiment is that a kind of zinc oxide nanowire array/foamy graphene composite material uses as working electrode, obtains the electric current of this material to variable concentrations L-3,4 dihydroxyphenylalanine corresponding thus play the effect detecting L-3,4 dihydroxyphenylalanine by the test of Pulse Voltammetry method.
Adopt following verification experimental verification effect of the present invention:
Test one: the preparation method of a kind of zinc oxide nanowire array/foamy graphene composite material of this test realizes by the following method:
One, chemical vapour deposition technique:
1) nickel foam is placed in quartz tube furnace central authorities, under the protection of argon gas and hydrogen, be heated to temperature from room temperature with the heating rate of 30 DEG C/min is 1000 DEG C, and be incubated 30min under the condition of 1000 DEG C in temperature, be in tubular furnace, pass into methane gas 10min with the speed of 10sccm under the condition of 1000 DEG C in temperature, then quartz tube furnace is 1000 DEG C with the cooldown rate of 100 DEG C/min from temperature and is cooled to room temperature, obtain the nickel foam of being wrapped up by Graphene; Step one 1) described in nickel foam density be 420g/m
2, thickness is 1.6mm; Step one 1) described in the flow velocity of argon gas be 500sccm, the flow velocity of hydrogen is 200sccm;
2) polymethylmethacrylate is dissolved in ethyl lactate, and be add thermal agitation 2h under the condition of 100 DEG C to obtain mixed solution in temperature, the use amount of 150 μ L is had to utilize sample loading gun that mixed solution is added drop-wise to step one 1 by every square centimeter) then the nickel foam of being wrapped up by the Graphene at room temperature natural drying on the surface that obtains is be incubated the foamy graphite alkene that 0.5h obtains Surface coating polymethylmethacrylate under the condition of 200 DEG C in temperature; Step one 2) described in mixed solution in the massfraction of methyl methacrylate be 4%;
3) by step one 2) to cut into surface area be 1cm for the foamy graphite alkene of Surface coating polymethylmethacrylate that obtains
2cube, and be soaked in that temperature is 90 DEG C completely, concentration is the three-dimensional foam Graphene that in the hydrochloric acid solution of 3mol/L, 5h obtains removing nickel;
4) by step one 3) to be soaked in temperature be 1h in the acetone of 60 DEG C for the three-dimensional foam Graphene of removal nickel that obtains, obtain the foamy graphite alkene removing polymethylmethacrylate, then with distilled water, the foamy graphite alkene removing polymethylmethacrylate is cleaned up, then the foamy graphite alkene of the removal polymethylmethacrylate cleaned up is transferred on clean ito glass, the use amount of 80 μ L is had to utilize sample loading gun to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up by zinc oxide seed layer solution by every square centimeter again, being placed in temperature is again be incubated 30min under the condition of 200 DEG C, obtain the three-dimensional foam Graphene/ito glass being prefabricated with zinc oxide seed layer, step one 4) described in clean ito glass be ito glass successively ultrasonic cleaning 15min, ultrasonic cleaning 15min and deionized water for ultrasonic cleaning 15min in ethanol in acetone successively, at room temperature natural drying obtains, step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methyl alcohol, then with the rotating speed magnetic agitation 5min of 500r/min, obtain zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.01mol/L,
Two, hydrothermal synthesis method:
1) zinc nitrate and hexamethylene tetramine are dissolved in deionized water, obtain hydro-thermal reaction solution with the rotating speed magnetic agitation 5min of 500r/min; Step 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.05mol/L; The concentration of hexamethylene tetramine is 0.05mol/L;
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) during the three-dimensional foam Graphene being prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in reactor mixed solution, cover reactor lid, 12h is reacted under the temperature conditions of 100 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain compound substance, open reactor distilled water compound substance is cleaned up, and 1h is incubated at 450 DEG C, cool to room temperature with the furnace, namely zinc oxide nanowire array/foamy graphene composite material is obtained.
Fig. 1 is the stereoscan photograph of the amplification 200 times of zinc oxide nanowire array/foamy graphene composite material prepared by test one; Fig. 2 is the stereoscan photograph of the amplification 500 times of zinc oxide nanowire array/foamy graphene composite material prepared by test one; Fig. 3 is the stereoscan photograph of the amplification 2000 times of zinc oxide nanowire array/foamy graphene composite material prepared by test one; Fig. 4 is the stereoscan photograph of the amplification 10000 times of zinc oxide nanowire array/foamy graphene composite material prepared by test one; Fig. 5 is the stereoscan photograph of the amplification 50000 times of zinc oxide nanowire array/foamy graphene composite material prepared by test one; Clearly can see that from figure oriented growth countless zinc oxide nano-wire arrays on three-dimensional grapheme, form zinc oxide nanowire array/foamy graphene three-dimensional composite material, zinc-oxide nano linear diameter is at ~ 80nm.
Fig. 6 is X ray diffracting spectrum, curve a is test one step one 4) in the X ray diffracting spectrum of the foamy graphite alkene of removal polymethylmethacrylate that cleans up, ● the diffraction peak of Graphene, obviously can find out the existence of Graphene diffraction peak from figure, illustrate that this material is pure Graphene; Curve b is the X ray diffracting spectrum of zinc oxide nanowire array/foamy graphene composite material prepared by test one, ● the diffraction peak of Graphene, ▲ be the diffraction peak of zinc paste, obviously can find out the existence of zinc paste and Graphene diffraction peak from figure, illustrate that this compound substance is made up of this bi-material.
Fig. 7 is test one step one 4) in the specific surface area curve of the foamy graphite alkene of removal polymethylmethacrylate that cleans up, curve a is adsorption curve, and curve b is desorption curve, and the specific surface area of this three-dimensional foam Graphene is 6m
2/ g; Fig. 8 is the specific surface area curve of zinc oxide nanowire array/foamy graphene composite material prepared by test one, and curve a is adsorption curve, and curve b is desorption curve, and the specific surface area of this compound substance reaches 22.7m
2/ g, specific surface area is comparatively large, and effective contact area is just large in the solution, thus also will improve the sensitivity detecting L-3,4 dihydroxyphenylalanine.
Test two: zinc oxide nanowire array/foamy graphene composite material is as the detection experiment of working electrode, and concrete operations are as follows:
Using zinc oxide nanowire array/foamy graphene composite material together with ito glass as working electrode, effective material area is 0.7cm
2, silver/silver chloride is as contrast electrode, and platinum filament, as to electrode, adopts traditional three-electrode system to be tested by Pulse Voltammetry method, and current potential increases 50mV, pulse height 4mV, sweep speed 8mV/s, thus it is corresponding to obtain the electric current of this material to variable concentrations L-3,4 dihydroxyphenylalanine; Described zinc oxide nanowire array/foamy graphene composite material is prepared by test one.
Utilize traditional three-electrode system to be detected by the test of Pulse Voltammetry method, obtain the figure of L-3,4 dihydroxyphenylalanine concentration and electric current linear fit.Fig. 9 is the Linear Fit Chart of the L-3,4 dihydroxyphenylalanine concentration that obtains of test two and electric current, by Fig. 9 in the concentration range of test, the linear relationship straight line of L-3,4 dihydroxyphenylalanine concentration change and electric current can be obtained, the sensitivity that namely L-3,4 dihydroxyphenylalanine concentration detect L-3,4 dihydroxyphenylalanine at 0.05 μm of ol/L ~ 1 μm straight slope that ol/L scope obtains is 2.2 μ A/ μm ol/L, and the detectability of L-3,4 dihydroxyphenylalanine reaches 50nmol/L.
Claims (7)
1. a preparation method for zinc oxide nanowire array/foamy graphene composite material, is characterized in that the preparation method of zinc oxide nanowire array/foamy graphene composite material carries out according to the following steps:
One, chemical vapour deposition technique:
1) nickel foam is placed in quartz tube furnace central authorities, under the protection of argon gas and hydrogen, be heated to temperature from room temperature with the 20 DEG C/min ~ 40 DEG C/heating rate of min is 1000 DEG C ~ 1100 DEG C, and be incubated 30min ~ 60min under the condition of 1000 DEG C ~ 1100 DEG C in temperature, be in tubular furnace, pass into methane gas 5min ~ 20min with the speed of 5sccm ~ 10sccm under the condition of 1000 DEG C ~ 1100 DEG C in temperature, then quartz tube furnace is 1000 DEG C ~ 1100 DEG C from temperature is cooled to room temperature with the 80 DEG C/min ~ 100 DEG C/cooldown rate of min, obtain the nickel foam of being wrapped up by Graphene, step one 1) described in nickel foam density be 420g/m
2~ 440g/m
2, thickness is 1.6mm ~ 2.0mm, step one 1) described in the flow velocity of argon gas be 480sccm ~ 500sccm, the flow velocity of hydrogen is 180sccm ~ 200sccm,
2) polymethylmethacrylate is dissolved in ethyl lactate, and be add thermal agitation 1h ~ 2h under the condition of 80 DEG C ~ 120 DEG C to obtain mixed solution in temperature, the use amount of 100 μ L ~ 200 μ L is had to utilize sample loading gun that mixed solution is added drop-wise to step one 1 by every square centimeter) nickel foam of being wrapped up by Graphene that obtains is on the surface, then at room temperature natural drying is be incubated the foamy graphite alkene that 0.5h ~ 1h obtains Surface coating polymethylmethacrylate under the condition of 150 DEG C ~ 200 DEG C in temperature; Step one 2) described in mixed solution in the massfraction of methyl methacrylate be 4% ~ 5%;
3) by step one 2) to cut into surface area be 0.5cm for the foamy graphite alkene of Surface coating polymethylmethacrylate that obtains
2~ 2cm
2cube, and be soaked in that temperature is 80 DEG C ~ 90 DEG C completely, concentration is the three-dimensional foam Graphene that in the hydrochloric acid solution of 3mol/L ~ 4mol/L, 4h ~ 6h obtains removing nickel;
4) by step one 3) to be soaked in temperature be 0.5h ~ 1.5h in the acetone of 60 DEG C ~ 70 DEG C for the three-dimensional foam Graphene of removal nickel that obtains, obtain the foamy graphite alkene removing polymethylmethacrylate, then with distilled water, the foamy graphite alkene removing polymethylmethacrylate is cleaned up, then the foamy graphite alkene of the removal polymethylmethacrylate cleaned up is transferred on clean ito glass, the use amount of 50 μ L ~ 100 μ L is had to utilize sample loading gun to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up by zinc oxide seed layer solution by every square centimeter again, being placed in temperature is again be incubated 20min ~ 30min under the condition of 150 DEG C ~ 200 DEG C, obtain the three-dimensional foam Graphene/ito glass being prefabricated with zinc oxide seed layer, step one 4) described in clean ito glass be ito glass successively ultrasonic cleaning 15min ~ 20min in acetone successively, ultrasonic cleaning 15min ~ 20min and deionized water for ultrasonic cleaning 15min ~ 20min in ethanol, at room temperature natural drying obtains, step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methyl alcohol, then with the rotating speed magnetic agitation 3min ~ 5min of 450r/min ~ 550r/min, obtain zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.001mol/L ~ 0.05mol/L,
Two, hydrothermal synthesis method:
1) zinc nitrate and hexamethylene tetramine are dissolved in deionized water, obtain hydro-thermal reaction solution with the rotating speed magnetic agitation 3min ~ 5min of 450r/min ~ 550r/min; Step 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.05mol/L ~ 0.1mol/L; The concentration of hexamethylene tetramine is 0.05mol/L ~ 0.1mol/L;
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) during the three-dimensional foam Graphene being prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in reactor mixed solution, cover reactor lid, 6h ~ 12h is reacted under the temperature conditions of 90 DEG C ~ 110 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain compound substance, open reactor distilled water compound substance is cleaned up, and 1h ~ 1.5h is incubated at 400 DEG C ~ 450 DEG C, cool to room temperature with the furnace, namely zinc oxide nanowire array/foamy graphene composite material is obtained.
2. the preparation method of a kind of zinc oxide nanowire array/foamy graphene composite material according to claim 1, it is characterized in that step one 1) in nickel foam is placed in quartz tube furnace central authorities, under the protection of argon gas and hydrogen, be heated to temperature from room temperature with the 25 DEG C/min ~ 35 DEG C/heating rate of min is 1000 DEG C ~ 1100 DEG C, and be incubated 40min ~ 50min under the condition of 1000 DEG C ~ 1100 DEG C in temperature, be in tubular furnace, pass into methane gas 10min ~ 15min with the speed of 7sccm ~ 9sccm under the condition of 1000 DEG C ~ 1100 DEG C in temperature, then quartz tube furnace is 1000 DEG C ~ 1100 DEG C from temperature is cooled to room temperature with the 85 DEG C/min ~ 95 DEG C/cooldown rate of min, obtain the nickel foam of being wrapped up by Graphene, step one 1) described in nickel foam density be 425g/m
2~ 435g/m
2, thickness is 1.6mm ~ 2.0mm, step one 1) described in the flow velocity of argon gas be 500sccm, the flow velocity of hydrogen is 200sccm.
3. the preparation method of a kind of zinc oxide nanowire array/foamy graphene composite material according to claim 1, it is characterized in that step one 2) in polymethylmethacrylate is dissolved in ethyl lactate, and be add thermal agitation 1h ~ 2h under the condition of 90 DEG C ~ 110 DEG C to obtain mixed solution in temperature, the use amount of 130 μ L ~ 170 μ L is had to utilize sample loading gun that mixed solution is added drop-wise to step one 1 by every square centimeter) nickel foam of being wrapped up by Graphene that obtains is on the surface, at room temperature natural drying, then be incubated the foamy graphite alkene that 0.5h ~ 1h obtains Surface coating polymethylmethacrylate under the condition of 150 DEG C ~ 200 DEG C in temperature, step one 2) described in mixed solution in the massfraction of methyl methacrylate be 4% ~ 5%.
4. the preparation method of a kind of zinc oxide nanowire array/foamy graphene composite material according to claim 1, is characterized in that step one 3) in by step one 2) to cut into surface area be 1.0cm for the foamy graphite alkene of Surface coating polymethylmethacrylate that obtains
2~ 1.5cm
2cube, and be soaked in that temperature is 80 DEG C ~ 90 DEG C completely, concentration is the three-dimensional foam Graphene that in the hydrochloric acid solution of 3mol/L ~ 4mol/L, 4.5h ~ 5.5h obtains removing nickel.
5. the preparation method of a kind of zinc oxide nanowire array/foamy graphene composite material according to claim 1, it is characterized in that step one 4) in by step one 3) to be soaked in temperature be 0.5h ~ 1.5h in the acetone of 60 DEG C ~ 70 DEG C for the three-dimensional foam Graphene of removal nickel that obtains, obtain the foamy graphite alkene removing polymethylmethacrylate, then with distilled water, the foamy graphite alkene removing polymethylmethacrylate is cleaned up, then the foamy graphite alkene of the removal polymethylmethacrylate cleaned up is transferred on clean ito glass, the use amount of 70 μ L ~ 90 μ L is had to utilize sample loading gun to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up by zinc oxide seed layer solution by every square centimeter again, being placed in temperature is again be incubated 20min ~ 30min under the condition of 170 DEG C ~ 190 DEG C, obtain the three-dimensional foam Graphene/ito glass being prefabricated with zinc oxide seed layer, step one 4) described in clean ito glass be ito glass successively ultrasonic cleaning 15min ~ 20min in acetone successively, ultrasonic cleaning 15min ~ 20min and deionized water for ultrasonic cleaning 15min ~ 20min in ethanol, at room temperature natural drying obtains, step one 4) described in zinc oxide seed layer solution prepare according to the following steps: zinc acetate is dissolved in methyl alcohol, then with the rotating speed magnetic agitation 3min ~ 5min of 450r/min ~ 550r/min, obtain zinc oxide seed layer solution, in wherein said zinc oxide seed layer solution, acetic acid zinc concentration is 0.005mol/L ~ 0.01mol/L.
6. the preparation method of a kind of zinc oxide nanowire array/foamy graphene composite material according to claim 1, is characterized in that step 2 1) described in hydro-thermal reaction solution in nitric acid zinc concentration be 0.06mol/L ~ 0.08mol/L; The concentration of hexamethylene tetramine is 0.06mol/L ~ 0.08mol/L.
7. the preparation method of a kind of zinc oxide nanowire array/foamy graphene composite material according to claim 1, it is characterized in that step 2 2) in by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step one 4) during the three-dimensional foam Graphene being prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in reactor mixed solution, cover reactor lid, 8h ~ 10h is reacted under the temperature conditions of 90 DEG C ~ 110 DEG C, then take out and naturally cool to room temperature in atmosphere, obtain compound substance, open reactor distilled water compound substance is cleaned up, and 1h ~ 1.5h is incubated at 420 DEG C ~ 440 DEG C, cool to room temperature with the furnace, namely zinc oxide nanowire array/foamy graphene composite material is obtained.
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