CN103482683A - Synthesis method of zinc oxide nano wire harness array/foam graphene composite material and application thereof - Google Patents
Synthesis method of zinc oxide nano wire harness array/foam graphene composite material and application thereof Download PDFInfo
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- CN103482683A CN103482683A CN201310479386.4A CN201310479386A CN103482683A CN 103482683 A CN103482683 A CN 103482683A CN 201310479386 A CN201310479386 A CN 201310479386A CN 103482683 A CN103482683 A CN 103482683A
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Abstract
The invention discloses a synthesis method of a zinc oxide nano wire harness array/foam graphene composite material and an application thereof, relating to a synthesis method of a composite material and an application thereof. The invention aims at solving the technical problems of low sensitivity and relatively high detection limit by applying the existing zinc oxide nano wire/foam graphene composite material to dopamine detection. The synthesis method comprises a chemical vapor deposition method and a hydrothermal synthesis method. The zinc oxide nano wire harness array/foam graphene composite material can be used as an electrode material to detect dopamine. The synthesis method disclosed by the invention is mainly used for synthesizing a zinc oxide nano wire harness array/foam graphene composite material.
Description
Technical field
The present invention relates to a kind of synthetic method and application thereof of matrix material.
Background technology
Graphene is a kind of two-dimensional material of only having a carbon atom thickness, and itself and zero dimension soccerballene, one dimension carbon nanotube, three-dimensional diamond and graphite form carbon nanometer family jointly.It has unusual conductivity, superelevation specific surface area, exceed the intensity of iron and steel decades of times and fabulous light transmission.The Andre Geim of Univ Manchester UK in 2004 and Konstantin Novoselov successfully separate stable Graphene first, thereby obtain Nobel Prize in physics in 2010.Document had been reported the synthetic method of multiple Graphene at present, and wherein application has mechanical stripping method, chemical oxidization method and chemical vapor deposition (CVD) method more widely.The mechanically peel method is the method that is applied to the earliest synthesizing graphite alkene, but the relatively low suitability for industrialized production that is unsuitable for of this method output; Chemical oxidization method is due to low cost and the large favor that is subject to many researchists of output, but a large amount of defects are contained in the Graphene inside that this method is produced, the residual a large amount of chemical groups in lamella edge, reduce its conductivity greatly, limited the application of the Graphene that this method produces; The synthetic Graphene electrical property superior with it of CVD method is subject to laboratory study personnel and Graphene manufacturer's approval, and the synthetic foamy graphite alkene of the method has few defect, high electric conductivity.Since within 2011, utilizing the high conductive foam Graphene of nickel foam synthetic three-dimensional, large porosity as the templated chemistry vapour deposition, this novel grapheme material has received very large concern, and the surface of this Graphene is also for metal oxide nano-material, combination provides good platform.
Nano zine oxide refers to a class special zinc oxide material of grain-size between 1nm～100nm, due to sharply reducing of grain-size, nano zine oxide shows the not available special property of many block materials, as non-migrating, fluorescence, piezoelectricity, absorption and scatters ultraviolet ability etc.Wherein one-dimension zinc oxide nano wire bundle array due to pattern low one of the most important research object of current field of nanometer material technology that becomes of controlled and production cost.The synthetic method of one-dimension zinc oxide nano wire bundle array has the methods such as chemical vapour deposition, physical vapor deposition and Hydrothermal Synthesis usually.Wherein to have a synthesis temperature low for hydrothermal synthesis method, with low cost and can large-scale production, therefore receives much concern.
Dopamine HCL (Dopamine, DA) chemical name is 3,4-dihydroxyl-β-phenylethylamine, it is a kind of important neurotransmitter extensively be present in vertebra and non-vertebrates, transmit pulse with helping cell, the DA deficiency can be made us the ability of muscle out of hand, when serious, can make patient's trick can't help earth tremor or cause Parkinson's disease.The content of Dopamine HCL in human body is very low, and the research of the content assaying method to it in brain, blood, urine and tissue is in physiological function research or all has important practical significance aspect clinical application.Only have at present one piece of article report zinc oxide nanowire/graphene composite material to be applied to Dopamine HCL and detect, and sensitivity very low be probably 0.015 μ A/ μ mol/L/cm
2higher with detectability is probably 10nmol/L, and how improving the sensitivity of sensor and reducing detectability becomes the task of top priority.
Summary of the invention
The present invention is the low and higher technical problem of detectability of sensitivity will solve existing zinc oxide nanowire/graphene composite material and be applied to Dopamine HCL and detect the time, thereby synthetic method and the application thereof of a kind of zinc oxide nano wire bundle array/foamy graphite alkene matrix material are provided.
The synthetic method of a kind of zinc oxide nano wire bundle array of the present invention/foamy graphite alkene matrix material is carried out according to the following steps:
One, chemical Vapor deposition process:
1) nickel foam is placed in to quartz tube furnace central authorities, take the temperature rise rate of 20 ℃/min～40 ℃/min from room temperature and be heated to temperature as 1000 ℃～1100 ℃ under the protection of argon gas and hydrogen, and be incubated 30min～60min under the condition that is 1000 ℃～1100 ℃ in temperature, pass into methane gas 5min～20min to the speed with 5sccm～10sccm in tube furnace under the condition that is 1000 ℃～1100 ℃ in temperature, then the rate of cooling of 80 ℃/min～100 ℃/min of quartz tube furnace being take is cooled to room temperature from temperature as 1000 ℃～1100 ℃, the nickel foam that obtains being wrapped up by Graphene, step 1 1) the nickel foam density described in is 420g/m
2～440g/m
2, thickness is 1.6mm～2.0mm, the flow velocity of the argon gas step 1 1) is 480sccm～500sccm, and the flow velocity of hydrogen is 180sccm～200sccm,
2) polymethylmethacrylate is dissolved in ethyl lactate, and under the condition that is 80 ℃～120 ℃ in temperature, heated and stirred 1h～2h obtains mixing solutions, by every square centimeter, have the usage quantity of 100 μ L～200 μ L to utilize sample loading gun that mixing solutions is added drop-wise to step 1 1) on the nickel foam of being wrapped up by Graphene that obtains, at room temperature seasoning, be incubated 0.5h～1h and obtain the foamy graphite alkene that surface coats polymethylmethacrylate under the condition that is then 150 ℃～200 ℃ in temperature; Step 1 2) in the mixing solutions described in, the massfraction of methyl methacrylate is 4%～5%;
3) by step 1 2) to cut into surface-area be 0.5cm to the surface that the obtains foamy graphite alkene that coats polymethylmethacrylate
2～2cm
2cubes, and to be soaked in temperature fully be the three-dimensional foam Graphene that in 80 ℃～90 ℃, the concentration hydrochloric acid soln that is 3mol/L～4mol/L, 4h～6h obtains removing nickel;
4) by step 1 3) the three-dimensional foam Graphene of the removal nickel that obtains is soaked in 0.5h～1.5h in the acetone that temperature is 60 ℃～70 ℃, obtain removing the foamy graphite alkene of polymethylmethacrylate, then the foamy graphite alkene that will remove polymethylmethacrylate with distilled water cleans up, the foamy graphite alkene of the removal polymethylmethacrylate that obtains cleaning up, then the foamy graphite alkene of the removal polymethylmethacrylate that cleans up is transferred on clean ito glass, by every square centimeter, there is the usage quantity of 50 μ L～100 μ L to utilize sample loading gun zinc oxide seed layer solution to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up again, be placed in again temperature and be under the condition of 150 ℃～200 ℃ and be incubated 20min～30min, obtain being prefabricated with the three-dimensional foam Graphene/ito glass of zinc oxide seed layer, step 1 4) the clean ito glass described in is ito glass priority ultrasonic cleaning 15min～20min in acetone successively, and in ethanol, ultrasonic cleaning 15min～20min and deionized water for ultrasonic are cleaned 15min～20min, and at room temperature seasoning obtains, step 1 4) the zinc oxide seed layer solution described in synthesizes according to the following steps: zinc acetate is dissolved in methyl alcohol, then with 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, the acetic acid zinc concentration is 0.001mol/L～0.05mol/L,
Two, hydrothermal synthesis method:
1) with distilled water as the vulkacit H solution of the solvent zinc nitrate solution that compound concentration is 0.01mol/L～0.1mol/L respectively, 0.01mol/L～0.1mol/L, the ammonia soln of 0.01mol/L～0.1mol/L and the polyetherimide amine aqueous solution of 5mmol/L～10mmol/L, and after four kinds of solution are mixed, the rotating speed magnetic agitation 3min～5min with 450r/min～550r/min obtains hydro-thermal reaction solution;
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step 1 4) the three-dimensional foam Graphene that is prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in the mixing solutions in reactor, cover the reactor lid, react 6h～12h under the temperature condition of 90 ℃～110 ℃, then take out and naturally cool to room temperature in air, obtain matrix material, opening reactor cleans up matrix material with distilled water, and be incubated 1h～1.5h under 400 ℃～450 ℃, cool to room temperature with the furnace, obtain zinc oxide nano wire bundle array/foamy graphite alkene matrix material.
The application of a kind of zinc oxide nano wire bundle array/foamy graphite alkene matrix material, zinc oxide nano wire bundle array/foamy graphite alkene matrix material is used as working electrode.
Advantage of the present invention:
(1) the inventive method synthesizes high electricity by chemical vapour deposition and leads flawless three-dimensional foam Graphene, the zinc oxide nano wire bundle array at Graphene surface growth high-specific surface area in conjunction with Hydrothermal Synthesis simultaneously, synthesized the zinc oxide nano wire bundle array of novel texture/three-dimensional foam graphene composite material;
(2) matrix material of the present invention can be brought into play the synergy that high electricity is led Graphene and high-specific surface area zinc oxide nano wire bundle array, the zinc oxide nano wire bundle array utilizes the synthetic combination that can improve zinc oxide and Graphene of Seed Layer, and the existence of zinc oxide nano wire bundle array, provide countless active sites on the Graphene surface, and the electronics that zinc oxide nanowire can directly produce reaction is delivered on Graphene, realize the fast transfer of electronics, therefore can significantly improve electrocatalysis characteristic, can make the sensitivity of Electrochemical Detection Dopamine HCL improve significantly to 4.3 μ A/ μ mol/L～13.9 μ A/ μ mol/L, and make the detectability of Dopamine HCL be reduced to 2nmol/L.
The accompanying drawing explanation
Fig. 1 is the stereoscan photograph of 500 times of the amplifications of test one synthetic zinc oxide nano wire bundle array/foamy graphite alkene matrix material;
Fig. 2 is the stereoscan photograph of 5000 times of the amplifications of test one synthetic zinc oxide nano wire bundle array/foamy graphite alkene matrix material;
Fig. 3 is the stereoscan photograph of 20000 times of the amplifications of test one synthetic zinc oxide nano wire bundle array/foamy graphite alkene matrix material;
Fig. 4 is the stereoscan photograph of 50000 times of the amplifications of test one synthetic zinc oxide nano wire bundle array/foamy graphite alkene matrix material;
Fig. 5 is the Raman collection of illustrative plates, curve a is test one step 1 4) in the Raman collection of illustrative plates of foamy graphite alkene of the removal polymethylmethacrylate that cleans up, curve b is the Raman collection of illustrative plates of the synthetic zinc oxide nano wire bundle array of test one/foamy graphite alkene matrix material, ● the peak of Graphene, ▲ be the peak of zinc oxide;
Fig. 6 is the Linear Fit Chart of test two dopamine concentrations that obtain and electric current.
Embodiment
Embodiment one: in present embodiment, the synthetic method of a kind of zinc oxide nano wire bundle array/foamy graphite alkene matrix material is carried out according to the following steps:
One, chemical Vapor deposition process:
1) nickel foam is placed in to quartz tube furnace central authorities, take the temperature rise rate of 20 ℃/min～40 ℃/min from room temperature and be heated to temperature as 1000 ℃～1100 ℃ under the protection of argon gas and hydrogen, and be incubated 30min～60min under the condition that is 1000 ℃～1100 ℃ in temperature, pass into methane gas 5min～20min to the speed with 5sccm～10sccm in tube furnace under the condition that is 1000 ℃～1100 ℃ in temperature, then the rate of cooling of 80 ℃/min～100 ℃/min of quartz tube furnace being take is cooled to room temperature from temperature as 1000 ℃～1100 ℃, the nickel foam that obtains being wrapped up by Graphene, step 1 1) the nickel foam density described in is 420g/m
2～440g/m
2, thickness is 1.6mm～2.0mm, the flow velocity of the argon gas step 1 1) is 480sccm～500sccm, and the flow velocity of hydrogen is 180sccm～200sccm,
2) polymethylmethacrylate is dissolved in ethyl lactate, and under the condition that is 80 ℃～120 ℃ in temperature, heated and stirred 1h～2h obtains mixing solutions, by every square centimeter, have the usage quantity of 100 μ L～200 μ L to utilize sample loading gun that mixing solutions is added drop-wise to step 1 1) on the nickel foam of being wrapped up by Graphene that obtains, be incubated 0.5h～1h under the condition that is then 150 ℃～200 ℃ in temperature and obtain the foamy graphite alkene that surface coats polymethylmethacrylate; Step 1 2) in the mixing solutions described in, the massfraction of methyl methacrylate is 4%～5%;
3) by step 1 2) to cut into surface-area be 0.5cm to the surface that the obtains foamy graphite alkene that coats polymethylmethacrylate
2～2cm
2cubes, and to be soaked in temperature fully be the three-dimensional foam Graphene that in 80 ℃～90 ℃, the concentration hydrochloric acid soln that is 3mol/L～4mol/L, 4h～6h obtains removing nickel;
4) by step 1 3) the three-dimensional foam Graphene of the removal nickel that obtains is soaked in 0.5h～1.5h in the acetone that temperature is 60 ℃～70 ℃, obtain removing the foamy graphite alkene of polymethylmethacrylate, then the foamy graphite alkene that will remove polymethylmethacrylate with distilled water cleans up, the foamy graphite alkene of the removal polymethylmethacrylate that obtains cleaning up, then the foamy graphite alkene of the removal polymethylmethacrylate that cleans up is transferred on clean ito glass, by every square centimeter, there is the usage quantity of 50 μ L～100 μ L to utilize sample loading gun zinc oxide seed layer solution to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up again, be placed in again temperature and be under the condition of 150 ℃～200 ℃ and be incubated 20min～30min, obtain being prefabricated with the three-dimensional foam Graphene/ito glass of zinc oxide seed layer, step 1 4) the clean ito glass described in is ito glass priority ultrasonic cleaning 15min～20min in acetone successively, and in ethanol, ultrasonic cleaning 15min～20min and deionized water for ultrasonic are cleaned 15min～20min, and at room temperature seasoning obtains, step 1 4) the zinc oxide seed layer solution described in synthesizes according to the following steps: zinc acetate is dissolved in methyl alcohol, then with 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, the acetic acid zinc concentration is 0.001mol/L～0.05mol/L,
Two, hydrothermal synthesis method:
1) with distilled water as the vulkacit H solution of the solvent zinc nitrate solution that compound concentration is 0.01mol/L～0.1mol/L respectively, 0.01mol/L～0.1mol/L, the ammonia soln of 0.01mol/L～0.1mol/L and the polyetherimide amine aqueous solution of 5mmol/L～10mmol/L, and after four kinds of solution are mixed, the rotating speed magnetic agitation 3min～5min with 450r/min～550r/min obtains hydro-thermal reaction solution;
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step 1 4) the three-dimensional foam Graphene that is prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in the mixing solutions in reactor, cover the reactor lid, react 6h～12h under the temperature condition of 90 ℃～110 ℃, then take out and naturally cool to room temperature in air, obtain matrix material, opening reactor cleans up matrix material with distilled water, and be incubated 1h～1.5h under 400 ℃～450 ℃, cool to room temperature with the furnace, obtain zinc oxide nano wire bundle array/foamy graphite alkene matrix material.
The advantage of present embodiment:
(1) the inventive method synthesizes high electricity by chemical vapour deposition and leads flawless three-dimensional foam Graphene, the zinc oxide nano wire bundle array at Graphene surface growth high-specific surface area in conjunction with Hydrothermal Synthesis simultaneously, synthesized the zinc oxide nano wire bundle array of novel texture/three-dimensional foam graphene composite material;
(2) matrix material of the present invention can be brought into play the synergy that high electricity is led Graphene and high-specific surface area zinc oxide nano wire bundle array, the zinc oxide nano wire bundle array utilizes the synthetic combination that can improve zinc oxide and Graphene of Seed Layer, and the existence of zinc oxide nano wire bundle array, provide countless active sites on the Graphene surface, and the electronics that zinc oxide nanowire can directly produce reaction is delivered on Graphene, realize the fast transfer of electronics, therefore can significantly improve electrocatalysis characteristic, can make the sensitivity of Electrochemical Detection Dopamine HCL improve significantly to 4.3 μ A/ μ mol/L～13.9 μ A/ μ mol/L, and make the detectability of Dopamine HCL be reduced to 2nmol/L.
Embodiment two: present embodiment is different from embodiment one: step 1 1), nickel foam is placed in to quartz tube furnace central authorities, take the temperature rise rate of 25 ℃/min～35 ℃/min from room temperature and be heated to temperature as 1000 ℃～1100 ℃ under the protection of argon gas and hydrogen, and be incubated 40min～50min under the condition that is 1000 ℃～1100 ℃ in temperature, pass into methane gas 10min～15min to the speed with 7sccm～9sccm in tube furnace under the condition that is 1000 ℃～1100 ℃ in temperature, then the rate of cooling of 85 ℃/min～95 ℃/min of quartz tube furnace being take is cooled to room temperature from temperature as 1000 ℃～1100 ℃, the nickel foam that obtains being wrapped up by Graphene, step 1 1) the nickel foam density described in is 425g/m
2～435g/m
2, thickness is 1.6mm～2.0mm, the flow velocity of the argon gas step 1 1) is 500sccm, and the flow velocity of hydrogen is 200sccm.Other is identical with embodiment one.
Embodiment three: present embodiment is different from one of embodiment one or two: step 1 2), polymethylmethacrylate is dissolved in ethyl lactate, and under the condition that is 90 ℃～110 ℃ in temperature, heated and stirred 1h～2h obtains mixing solutions, by every square centimeter, have the usage quantity of 130 μ L～170 μ L to utilize sample loading gun that mixing solutions is added drop-wise to step 1 1) on the nickel foam of being wrapped up by Graphene that obtains, at room temperature seasoning, then be incubated 0.5h～1h under the condition that is 150 ℃～200 ℃ in temperature and obtain the foamy graphite alkene that surface coats polymethylmethacrylate, step 1 2) in the mixing solutions described in, the massfraction of methyl methacrylate is 4%～5%.Other is identical with one of embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: step 1 3) by step 1 2) to cut into surface-area be 1.0cm to the surface that the obtains foamy graphite alkene that coats polymethylmethacrylate
2～1.5cm
2cubes, and to be soaked in temperature fully be the three-dimensional foam Graphene that in 80 ℃～90 ℃, the concentration hydrochloric acid soln that is 3mol/L～4mol/L, 4.5h～5.5h obtains removing nickel.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: step 1 4) by step 1 3) the three-dimensional foam Graphene of the removal nickel that obtains is soaked in 0.5h～1.5h in the acetone that temperature is 60 ℃～70 ℃, obtain removing the foamy graphite alkene of polymethylmethacrylate, then the foamy graphite alkene that will remove polymethylmethacrylate with distilled water cleans up, the foamy graphite alkene of the removal polymethylmethacrylate that obtains cleaning up, then the foamy graphite alkene of the removal polymethylmethacrylate that cleans up is transferred on clean ito glass, by every square centimeter, there is the usage quantity of 70 μ L～90 μ L to utilize sample loading gun zinc oxide seed layer solution to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up again, be placed in again temperature and be under the condition of 170 ℃～190 ℃ and be incubated 20min～30min, obtain being prefabricated with the three-dimensional foam Graphene/ito glass of zinc oxide seed layer, step 1 4) the clean ito glass described in is ito glass priority ultrasonic cleaning 15min～20min in acetone successively, and in ethanol, ultrasonic cleaning 15min～20min and deionized water for ultrasonic are cleaned 15min～20min, and at room temperature seasoning obtains, step 1 4) the zinc oxide seed layer solution described in synthesizes according to the following steps: zinc acetate is dissolved in methyl alcohol, then with 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, the acetic acid zinc concentration is 0.005mol/L～0.01mol/L.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: step 2 1) with distilled water as the vulkacit H solution of the solvent zinc nitrate solution that compound concentration is 0.02mol/L～0.06mol/L respectively, 0.02mol/L～0.06mol/L, the ammonia soln of 0.02mol/L～0.06mol/L and the polyetherimide amine aqueous solution of 7mmol/L～9mmol/L, and after four kinds of solution are mixed, the rotating speed magnetic agitation 3min～5min with 450r/min～550r/min obtains hydro-thermal reaction solution.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: step 2 2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step 1 4) the three-dimensional foam Graphene that is prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in the mixing solutions in reactor, cover the reactor lid, react 8h～10h under the temperature condition of 90 ℃～110 ℃, then take out and naturally cool to room temperature in air, obtain matrix material, opening reactor cleans up matrix material with distilled water, and be incubated 1h～1.5h under 420 ℃～440 ℃, cool to room temperature with the furnace, obtain zinc oxide nano wire bundle array/foamy graphite alkene matrix material.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is the application of a kind of zinc oxide nano wire bundle array/foamy graphite alkene matrix material, and zinc oxide nano wire bundle array/foamy graphite alkene matrix material is used as working electrode.
Present embodiment is that a kind of zinc oxide nano wire bundle array/foamy graphite alkene matrix material is used as working electrode, thereby obtains this material to the corresponding effect of playing the detection Dopamine HCL of the electric current of different concns Dopamine HCL by the test of Pulse Voltammetry method.
Adopt following verification experimental verification effect of the present invention:
Test one: the synthetic method of a kind of zinc oxide nano wire bundle array of this test/foamy graphite alkene matrix material is to realize by the following method:
One, chemical Vapor deposition process:
1) nickel foam is placed in to quartz tube furnace central authorities, take the temperature rise rate of 30 ℃/min from room temperature and be heated to temperature as 1000 ℃ under the protection of argon gas and hydrogen, and be incubated 30min under the condition that is 1000 ℃ in temperature, pass into methane gas 10min to the speed with 10sccm in tube furnace under the condition that is 1000 ℃ in temperature, then the rate of cooling of 100 ℃/min of quartz tube furnace being take is cooled to room temperature, the nickel foam that obtains being wrapped up by Graphene from temperature as 1000 ℃; Step 1 1) the nickel foam density described in is 420g/m
2, thickness is 1.6mm; The flow velocity of the argon gas step 1 1) is 500sccm, and the flow velocity of hydrogen is 200sccm;
2) polymethylmethacrylate is dissolved in ethyl lactate, and under the condition that is 100 ℃ in temperature, heated and stirred 2h obtains mixing solutions, by every square centimeter, have the usage quantity of 150 μ L to utilize sample loading gun that mixing solutions is added drop-wise to step 1 1) on the nickel foam of being wrapped up by Graphene that obtains, at room temperature seasoning, under the condition that is then 200 ℃ in temperature, insulation 0.5h obtains the foamy graphite alkene that surface coats polymethylmethacrylate; Step 1 2) in the mixing solutions described in, the massfraction of methyl methacrylate is 4%;
3) by step 1 2) to cut into surface-area be 1cm to the surface that the obtains foamy graphite alkene that coats polymethylmethacrylate
2cubes, and to be soaked in temperature fully be the three-dimensional foam Graphene that in 90 ℃, the concentration hydrochloric acid soln that is 3mol/L, 5h obtains removing nickel;
4) by step 1 3) the three-dimensional foam Graphene of the removal nickel that obtains is soaked in 1h in the acetone that temperature is 60 ℃, obtain removing the foamy graphite alkene of polymethylmethacrylate, then the foamy graphite alkene that will remove polymethylmethacrylate with distilled water cleans up, the foamy graphite alkene of the removal polymethylmethacrylate that obtains cleaning up, then the foamy graphite alkene of the removal polymethylmethacrylate that cleans up is transferred on clean ito glass, by every square centimeter, there is the usage quantity of 80 μ L to utilize sample loading gun zinc oxide seed layer solution to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up again, be incubated 30min under the condition that to be placed in temperature be 200 ℃ again, obtain being prefabricated with the three-dimensional foam Graphene/ito glass of zinc oxide seed layer, step 1 4) the clean ito glass described in is ito glass priority ultrasonic cleaning 15min in acetone successively, and in ethanol, ultrasonic cleaning 15min and deionized water for ultrasonic are cleaned 15min, and at room temperature seasoning obtains, step 1 4) the zinc oxide seed layer solution described in synthesizes 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, the acetic acid zinc concentration is 0.01mol/L,
Two, hydrothermal synthesis method:
1) with distilled water as the vulkacit H solution of the solvent zinc nitrate solution that compound concentration is 0.025mol/L respectively, 0.025mol/L, the ammonia soln of 0.025mol/L and the polyetherimide amine aqueous solution of 5mmol/L, and after four kinds of solution are mixed, the rotating speed magnetic agitation 5min with 500r/min obtains hydro-thermal reaction solution;
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step 1 4) the three-dimensional foam Graphene that is prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in the mixing solutions in reactor, cover the reactor lid, react 12h under the temperature condition of 100 ℃, then take out and naturally cool to room temperature in air, obtain matrix material, opening reactor cleans up matrix material with distilled water, and be incubated 1h under 450 ℃, cool to room temperature with the furnace, obtain zinc oxide nano wire bundle array/foamy graphite alkene matrix material.
Fig. 1 is the stereoscan photograph of 500 times of the amplifications of test one synthetic zinc oxide nano wire bundle array/foamy graphite alkene matrix material; Fig. 2 is the stereoscan photograph of 5000 times of the amplifications of test one synthetic zinc oxide nano wire bundle array/foamy graphite alkene matrix material; Fig. 3 is the stereoscan photograph of 20000 times of the amplifications of test one synthetic zinc oxide nano wire bundle array/foamy graphite alkene matrix material; Fig. 4 is the stereoscan photograph of 50000 times of the amplifications of test one synthetic zinc oxide nano wire bundle array/foamy graphite alkene matrix material; Can clearly see that from figure oriented growth countless zinc oxide nano wire bundle arrays on three-dimensional grapheme, form zinc oxide nano wire bundle array/foamy graphite alkene three-dimensional composite material.
Fig. 5 is the Raman collection of illustrative plates, curve a is test one step 1 4) in the Raman collection of illustrative plates of foamy graphite alkene of the removal polymethylmethacrylate that cleans up, as can be seen from the figure Graphene has obvious G band and 2D band, the D band does not appear, show that Graphene is flawless, the strength ratio of G band and 2D band shows that synthetic Graphene is multilayer; Curve b is the Raman collection of illustrative plates of the synthetic zinc oxide nano wire bundle array of test one/foamy graphite alkene matrix material, ● the peak of Graphene, ▲ be the peak of zinc oxide, as can be seen from the figure this matrix material is except G band and 2D band that Graphene is arranged, also have the peak of zinc oxide, also show that this matrix material has this bi-material set to form.
Test two: zinc oxide nano wire bundle array/foamy graphite alkene matrix material is as the detection test of working electrode, and concrete operations are as follows:
Using zinc oxide nano wire bundle array/foamy graphite alkene matrix material together with ito glass as working electrode, effectively material area is 0.7cm
2, silver/silver chloride is as reference electrode, and platinum filament, as to electrode, adopts traditional three-electrode system by the test of Pulse Voltammetry method, and current potential increases 50mV, pulse height 4mV, scanning speed 8mV/s, thus it is corresponding to the electric current of different concns Dopamine HCL to obtain this material; Described zinc oxide nano wire bundle array/foamy graphite alkene matrix material is that test one is synthetic.
Utilize traditional three-electrode system to be detected by the test of Pulse Voltammetry method, obtain dopamine concentration and electric current linear fit.Fig. 6 is the Linear Fit Chart of test two dopamine concentrations that obtain and electric current, by Fig. 6 the test concentration range in, can obtain two linear relationship straight lines of dopamine concentration variation and electric current, the sensitivity that dopamine concentration detects Dopamine HCL at the straight slope that 0.01 μ mol/L～0.1 μ mol/L scope obtains is 13.9 μ A/ μ mol/L, and the sensitivity that dopamine concentration detects Dopamine HCL at the straight slope that 0.1 μ mol/L～1 μ mol/L scope obtains is 4.3 μ A/ μ mol/L; The detectability of Dopamine HCL has reached 2nmol/L.
Claims (8)
1. the synthetic method of zinc oxide nano wire bundle array/foamy graphite alkene matrix material is characterized in that the synthetic method of zinc oxide nano wire bundle array/foamy graphite alkene matrix material is carried out according to the following steps:
One, chemical Vapor deposition process:
1) nickel foam is placed in to quartz tube furnace central authorities, take the temperature rise rate of 20 ℃/min～40 ℃/min from room temperature and be heated to temperature as 1000 ℃～1100 ℃ under the protection of argon gas and hydrogen, and be incubated 30min～60min under the condition that is 1000 ℃～1100 ℃ in temperature, pass into methane gas 5min～20min to the speed with 5sccm～10sccm in tube furnace under the condition that is 1000 ℃～1100 ℃ in temperature, then the rate of cooling of 80 ℃/min～100 ℃/min of quartz tube furnace being take is cooled to room temperature from temperature as 1000 ℃～1100 ℃, the nickel foam that obtains being wrapped up by Graphene, step 1 1) the nickel foam density described in is 420g/m
2～440g/m
2, thickness is 1.6mm～2.0mm, the flow velocity of the argon gas step 1 1) is 480sccm～500sccm, and the flow velocity of hydrogen is 180sccm～200sccm,
2) polymethylmethacrylate is dissolved in ethyl lactate, and under the condition that is 80 ℃～120 ℃ in temperature, heated and stirred 1h～2h obtains mixing solutions, by every square centimeter, have the usage quantity of 100 μ L～200 μ L to utilize sample loading gun that mixing solutions is added drop-wise to step 1 1) on the nickel foam of being wrapped up by Graphene that obtains, at room temperature seasoning, be incubated 0.5h～1h and obtain the foamy graphite alkene that surface coats polymethylmethacrylate under the condition that is then 150 ℃～200 ℃ in temperature; Step 1 2) in the mixing solutions described in, the massfraction of methyl methacrylate is 4%～5%;
3) by step 1 2) to cut into surface-area be 0.5cm to the surface that the obtains foamy graphite alkene that coats polymethylmethacrylate
2～2cm
2cubes, and to be soaked in temperature fully be the three-dimensional foam Graphene that in 80 ℃～90 ℃, the concentration hydrochloric acid soln that is 3mol/L～4mol/L, 4h～6h obtains removing nickel;
4) by step 1 3) the three-dimensional foam Graphene of the removal nickel that obtains is soaked in 0.5h～1.5h in the acetone that temperature is 60 ℃～70 ℃, obtain removing the foamy graphite alkene of polymethylmethacrylate, then the foamy graphite alkene that will remove polymethylmethacrylate with distilled water cleans up, the foamy graphite alkene of the removal polymethylmethacrylate that obtains cleaning up, then the foamy graphite alkene of the removal polymethylmethacrylate that cleans up is transferred on clean ito glass, by every square centimeter, there is the usage quantity of 50 μ L～100 μ L to utilize sample loading gun zinc oxide seed layer solution to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up again, be placed in again temperature and be under the condition of 150 ℃～200 ℃ and be incubated 20min～30min, obtain being prefabricated with the three-dimensional foam Graphene/ito glass of zinc oxide seed layer, step 1 4) the clean ito glass described in is ito glass priority ultrasonic cleaning 15min～20min in acetone successively, and in ethanol, ultrasonic cleaning 15min～20min and deionized water for ultrasonic are cleaned 15min～20min, and at room temperature seasoning obtains, step 1 4) the zinc oxide seed layer solution described in synthesizes according to the following steps: zinc acetate is dissolved in methyl alcohol, then with 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, the acetic acid zinc concentration is 0.001mol/L～0.05mol/L,
Two, hydrothermal synthesis method:
1) with distilled water as the vulkacit H solution of the solvent zinc nitrate solution that compound concentration is 0.01mol/L～0.1mol/L respectively, 0.01mol/L～0.1mol/L, the ammonia soln of 0.01mol/L～0.1mol/L and the polyetherimide amine aqueous solution of 5mmol/L～10mmol/L, and after four kinds of solution are mixed, the rotating speed magnetic agitation 3min～5min with 450r/min～550r/min obtains hydro-thermal reaction solution;
2) by step 2 1) the hydro-thermal reaction solution that obtains pours in reactor, then by step 1 4) the three-dimensional foam Graphene that is prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in the mixing solutions in reactor, cover the reactor lid, react 6h～12h under the temperature condition of 90 ℃～110 ℃, then take out and naturally cool to room temperature in air, obtain matrix material, opening reactor cleans up matrix material with distilled water, and be incubated 1h～1.5h under 400 ℃～450 ℃, cool to room temperature with the furnace, obtain zinc oxide nano wire bundle array/foamy graphite alkene matrix material.
2. the synthetic method of a kind of zinc oxide nano wire bundle array according to claim 1/foamy graphite alkene matrix material, it is characterized in that step 1 1) in nickel foam is placed in to quartz tube furnace central authorities, take the temperature rise rate of 25 ℃/min～35 ℃/min from room temperature and be heated to temperature as 1000 ℃～1100 ℃ under the protection of argon gas and hydrogen, and be incubated 40min～50min under the condition that is 1000 ℃～1100 ℃ in temperature, pass into methane gas 10min～15min to the speed with 7sccm～9sccm in tube furnace under the condition that is 1000 ℃～1100 ℃ in temperature, then the rate of cooling of 85 ℃/min～95 ℃/min of quartz tube furnace being take is cooled to room temperature from temperature as 1000 ℃～1100 ℃, the nickel foam that obtains being wrapped up by Graphene, step 1 1) the nickel foam density described in is 425g/m
2～435g/m
2, thickness is 1.6mm～2.0mm, the flow velocity of the argon gas step 1 1) is 500sccm, and the flow velocity of hydrogen is 200sccm.
3. the synthetic method of a kind of zinc oxide nano wire bundle array according to claim 1/foamy graphite alkene matrix material, it is characterized in that step 1 2) in polymethylmethacrylate is dissolved in ethyl lactate, and under the condition that is 90 ℃～110 ℃ in temperature, heated and stirred 1h～2h obtains mixing solutions, by every square centimeter, have the usage quantity of 130 μ L～170 μ L to utilize sample loading gun that mixing solutions is added drop-wise to step 1 1) on the nickel foam of being wrapped up by Graphene that obtains, at room temperature seasoning, then be incubated 0.5h～1h under the condition that is 150 ℃～200 ℃ in temperature and obtain the foamy graphite alkene that surface coats polymethylmethacrylate, step 1 2) in the mixing solutions described in, the massfraction of methyl methacrylate is 4%～5%.
4. the synthetic method of a kind of zinc oxide nano wire bundle array according to claim 1/foamy graphite alkene matrix material, is characterized in that step 1 3) in by step 1 2) to cut into surface-area be 1.0cm to the surface that the obtains foamy graphite alkene that coats polymethylmethacrylate
2～1.5cm
2cubes, and to be soaked in temperature fully be the three-dimensional foam Graphene that in 80 ℃～90 ℃, the concentration hydrochloric acid soln that is 3mol/L～4mol/L, 4.5h～5.5h obtains removing nickel.
5. the synthetic method of a kind of zinc oxide nano wire bundle array according to claim 1/foamy graphite alkene matrix material, it is characterized in that step 1 4) in by step 1 3) the three-dimensional foam Graphene of the removal nickel that obtains is soaked in 0.5h～1.5h in the acetone that temperature is 60 ℃～70 ℃, obtain removing the foamy graphite alkene of polymethylmethacrylate, then the foamy graphite alkene that will remove polymethylmethacrylate with distilled water cleans up, the foamy graphite alkene of the removal polymethylmethacrylate that obtains cleaning up, then the foamy graphite alkene of the removal polymethylmethacrylate that cleans up is transferred on clean ito glass, by every square centimeter, there is the usage quantity of 70 μ L～90 μ L to utilize sample loading gun zinc oxide seed layer solution to be added drop-wise on the foamy graphite alkene of the removal polymethylmethacrylate cleaned up again, be placed in again temperature and be under the condition of 170 ℃～190 ℃ and be incubated 20min～30min, obtain being prefabricated with the three-dimensional foam Graphene/ito glass of zinc oxide seed layer, step 1 4) the clean ito glass described in is ito glass priority ultrasonic cleaning 15min～20min in acetone successively, and in ethanol, ultrasonic cleaning 15min～20min and deionized water for ultrasonic are cleaned 15min～20min, and at room temperature seasoning obtains, step 1 4) the zinc oxide seed layer solution described in synthesizes according to the following steps: zinc acetate is dissolved in methyl alcohol, then with 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, the acetic acid zinc concentration is 0.005mol/L～0.01mol/L.
6. the synthetic method of a kind of zinc oxide nano wire bundle array according to claim 1/foamy graphite alkene matrix material, it is characterized in that step 2 1) in distilled water as the vulkacit H solution of the solvent zinc nitrate solution that compound concentration is 0.02mol/L～0.06mol/L respectively, 0.02mol/L～0.06mol/L, the ammonia soln of 0.02mol/L～0.06mol/L and the polyetherimide amine aqueous solution of 7mmol/L～9mmol/L, and after four kinds of solution are mixed, the rotating speed magnetic agitation 3min～5min with 450r/min～550r/min obtains hydro-thermal reaction solution.
7. the synthetic method of a kind of zinc oxide nano wire bundle array according to claim 1/foamy graphite alkene matrix material, 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 1 4) the three-dimensional foam Graphene that is prefabricated with zinc oxide seed layer that obtains/ito glass stands upside down and is positioned in the mixing solutions in reactor, cover the reactor lid, react 8h～10h under the temperature condition of 90 ℃～110 ℃, then take out and naturally cool to room temperature in air, obtain matrix material, opening reactor cleans up matrix material with distilled water, and be incubated 1h～1.5h under 420 ℃～440 ℃, cool to room temperature with the furnace, obtain zinc oxide nano wire bundle array/foamy graphite alkene matrix material.
8. the application of zinc oxide nano wire bundle array/foamy graphite alkene matrix material, is characterized in that zinc oxide nano wire bundle array/foamy graphite alkene matrix material is used as working electrode.
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