CN103529099B - A kind of growth in situ prepares the method for Graphene chemically modified electrode - Google Patents
A kind of growth in situ prepares the method for Graphene chemically modified electrode Download PDFInfo
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Abstract
The invention discloses a kind of method that growth in situ prepares Graphene chemically modified electrode, its way mainly: A, substrate cleaning；B, growth in situ Graphene: the substrate that A step obtains is placed in clean quartz boat, and quartz boat is placed in the quartz ampoule of horizontal resistance furnace；First logical argon removes the oxygen in quartz ampoule, then under the protection of argon, quartz ampoule is heated to the growth temperature of Graphene；Then it is incubated 1～180min, changes logical carbon-source gas and hydrogen when insulation；Subsequently, being cooled to room temperature under the protection of argon, namely taking-up obtains growth in situ the substrate of Graphene；C, there is the substrate of Graphene connect upper conductor or be directly placed in fixture the B growth in situ that obtains of step, obtain Graphene chemically modified electrode.The preparation process of the method the method is succinct, and preparation efficiency is high, suitable for mass production；And the Graphene chemically modified electrode prepared, quality is good, detection function admirable.
Description
Technical field
The present invention relates to a kind of method that growth in situ prepares Graphene chemically modified electrode.
Background technology
2004, Univ Manchester UK physicist AndreGeim and KonstantinNovoselov, successfully utilize adhesive tape stripping method to isolate single-layer graphene from graphite in the lab.Through concentrating on studies of nearly 10 years of world wide internal medicine worker, it was demonstrated that Graphene is the thinnest in the world at present is also the hardest nano material, has high heat conductivity and electron mobility and stable chemical stability and light transmittance.It is made to have application prospect widely in the field such as electrochemistry, photoelectron.Namely Graphene chemically modified electrode is a kind of modified electrode of the electrochemical performance utilizing Graphene to make, and its superiority is mainly manifested in can accelerate electron transfer speed, strengthens response current, reduces detection limit etc..
The preparation method of Graphene chemically modified electrode conventional at present is: utilizes methane for carbon source, prepares high-quality single or multiple lift Graphene with chemical vapour deposition technique on nickel or Copper Foil substrate；An attached strata methyl methacrylate protecting film on Graphene, separates, followed by electrochemistry or chemical method, the Graphene being grown in nickel or copper substrate surfaces and obtains the solution containing Graphene again；Finally, by containing Graphene solution drip on existing electrode surface, solvent volatilization after, Graphene with regard to load at electrode surface, thus obtaining Graphene chemically modified electrode.This method is that the growth first passing through Graphene obtains Graphene, then by Graphene stripping, load at electrode surface；Its preparation process is complicated, and when stripping and load Graphene, can destroy the unique texture of itself, affect the performance of the excellent detection performance of Graphene.
Summary of the invention
It is an object of the invention to provide a kind of method that growth in situ prepares Graphene chemically modified electrode, the preparation process of the method is succinct, and preparation efficiency is high, suitable for mass production；And the Graphene chemically modified electrode prepared, quality is good, detection function admirable.
The present invention realizes a kind of method that its goal of the invention be the technical scheme is that growth in situ prepares Graphene chemically modified electrode, the steps include:
A, substrate cleaning
Substrate is sequentially placed into acetone, dehydrated alcohol and secondary deionized water ultrasonic cleaning, to remove greasy dirt and other impurity on its surface；Then, substrate is placed in air dry oven and dries, stand-by；
B, growth in situ Graphene
The substrate that A step obtains is placed in clean quartz boat, and quartz boat is placed in the quartz ampoule of horizontal resistance furnace；First logical argon removes the oxygen in quartz ampoule, then under the protection of argon, quartz ampoule is heated to the growth temperature of Graphene；Then it is incubated 1～180min, changes logical carbon-source gas and hydrogen when insulation；Subsequently, being cooled to room temperature under the protection of argon, namely taking-up obtains growth in situ the substrate of Graphene；
C, chemically modified electrode preparation
The substrate that the growth in situ that B step obtains has Graphene is connected upper conductor or is directly placed in fixture, obtains Graphene chemically modified electrode.
The substrate of above-mentioned A step is quartz glass plate or SiO2/ Si sheet.
One or more the mixture that carbon-source gas is acetylene, methane, ethylene, acetylene in above-mentioned B step.
The growth temperature of the Graphene in above-mentioned B step is 600～1200 DEG C.
Carbon-source gas and the volume ratio of hydrogen in above-mentioned B step are 1:1～100.
The principle of the inventive method is:
Carbon-source gas, when the growth temperature of Graphene, is decomposed into carbon atom and the hydrogen atom of free radical.Carbon atom is polymerized and forms graphite flake layer, and meanwhile, the hydrogen atom of free state has extremely strong activity can etch away the carbon-carbon bond that bond energy is more weak；Under the combined effect of both processes, substrate grows into graphene film.Owing to Graphene has good electric conductivity, the continuous print graphene film at substrate surface makes it have electric conductivity.Therefore, the substrate of insulation, after graphene modified, can be directly used for Electrochemical Detection and becomes Graphene chemically modified electrode.
Compared with the conventional method, the invention has the beneficial effects as follows:
One, with first generate Graphene peel off again, compared with load Graphene method in electrode basement, the Graphene growth in situ of the present invention, in nonconducting substrate, directly obtains Graphene chemically modified electrode, it is simple to operate, one step completes, and preparation efficiency is high, suitable for mass production.
Two, Graphene growth in situ is directly prepared into chemically modified electrode in nonconducting substrate, it also avoid stripping and the transfer process destruction to Graphene unique texture, keeping the perfect pattern after graphene growth, prepared Graphene chemically modified electrode quality is good, detection function admirable.
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further detailed explanation.
Accompanying drawing explanation
Fig. 1 is the digital photograph of substrate-quartz glass plate that embodiment one adopts.
Fig. 2 is the digital photograph of the Graphene that embodiment one step growth goes out.
Fig. 3 A is the embodiment one B 1000 times of scanning electron microscope (SEM) photographs walking the Graphene that growth in situ goes out.
Fig. 3 B is the embodiment one B 10000 times of scanning electron microscope (SEM) photographs walking the Graphene that growth in situ goes out.
Fig. 4 is the I-V curve figure of the Graphene chemically modified electrode that embodiment one obtains.
Fig. 5 is that Graphene chemically modified electrode difference in 1MKCl solution that embodiment one obtains sweeps the cyclic voltammetry curve under speed.
Fig. 6 is that the Graphene chemically modified electrode that obtains of embodiment one is at 0.001MK3Fe(CN)6+0.001MK4Fe(CN)6Cyclic voltammetry curve in+1MKCl solution, under different voltage scan rate.
Fig. 7 is the Graphene chemically modified electrode that embodiment one obtains, at 0.001MK3Fe(CN)6+0.001MK4Fe(CN)6The subduplicate curve to scanning speed of the subduplicate curve to scanning speed of the oxidation peak current in+1MKCl solution and reduction peak current and scanning speed.Wherein, symbol " " curve strung is the oxidation peak current subduplicate curve to scanning speed, symbol "●" the curve strung is the reduction peak current subduplicate curve to scanning speed.
Fig. 8 is the Graphene chemically modified electrode that embodiment one obtains, at 0.001MK3Fe(CN)6+0.001MK4Fe(CN)6The oxidoreduction spike potential difference in+1MKCl solution subduplicate curve to scanning speed.
Detailed description of the invention
Embodiment one
A kind of detailed description of the invention of the present invention is that a kind of growth in situ prepares the method for Graphene chemically modified electrode, the steps include:
A, substrate cleaning
Quartz glass plate is sequentially placed in acetone, dehydrated alcohol and secondary deionized water and distinguishes ultrasonic cleaning 10min, to remove greasy dirt and other impurity on its surface；Then, quartz glass plate is placed in air dry oven and dries.
B, growth in situ Graphene
The quartz glass plate that A step obtains is placed in clean quartz boat, and quartz boat is placed in the quartz ampoule of horizontal resistance furnace；First logical argon removes the oxygen in quartz ampoule, then under the protection of argon, quartz ampoule is heated to 900 DEG C；Then being incubated 10min, change logical acetylene and hydrogen when insulation, wherein the volume ratio of acetylene and hydrogen is 1:10；Subsequently, being cooled to room temperature under the protection of argon, namely taking-up obtains growth in situ the substrate of Graphene；
C, chemically modified electrode preparation
There is the substrate of Graphene to be directly placed in fixture the growth in situ that B step obtains, obtain Graphene chemically modified electrode.
Fig. 1 is the digital photograph of substrate-quartz glass plate that embodiment one adopts.As seen from Figure 1, any surface finish of quartz glass plate is smooth.
Fig. 2 is the digital photograph of the Graphene that embodiment one step growth goes out.From Figure 2 it can be seen that the Graphene being grown on quartz glass has metallic luster, there is fabulous reflective simultaneously.
Fig. 3 A and Fig. 3 B respectively embodiment one B walks 1000 times and 10000 times of scanning electron microscope (SEM) photographs of the Graphene that growth in situ goes out.From Fig. 3 A, the Graphene on quartz glass is overlapping lamellar structure, and from Fig. 3 B, the Graphene on quartz glass plate has bigger monolithic area and its smooth surface is smooth.
Fig. 4 is the I-V curve figure of the Graphene chemically modified electrode that embodiment one obtains.From fig. 4, it can be seen that the voltage being applied on Graphene and response current have good linear relationship, it was shown that on quartz glass, the Graphene of growth in situ has stable electric property.
Fig. 5 is Graphene chemically modified electrode cyclic voltammetry curve under different voltage scanning speed in 1MKCl solution that embodiment one obtains.As seen from Figure 5, along with sweep speed increase, its current-responsive increases accordingly, but its each current values is all only small, also without oxidoreduction peak occur.
Fig. 6 is the Graphene chemically modified electrode that embodiment one obtains, at 0.001MK3Fe(CN)6+0.001MK4Fe(CN)6With the cyclic voltammetry curve under different scanning speed in+1MKCl solution.As seen from Figure 6, the cyclic voltammetry curve of the Graphene chemically modified electrode of growth in situ has obvious oxidoreduction peak, and, along with the raising of scanning speed, current-responsive is further obvious.Additionally, oxidoreduction spike potential difference increases also with the increase of scanning speed.
Fig. 7 is the Graphene chemically modified electrode that embodiment one obtains, at 0.001MK3Fe(CN)6+0.001MK4Fe(CN)6The subduplicate curve to scanning speed of the subduplicate curve to scanning speed of the oxidation peak current in+1MKCl solution and reduction peak current and scanning speed.Wherein, symbol " " curve strung is the oxidation peak current subduplicate curve to scanning speed, symbol "●" the curve strung is the reduction peak current subduplicate curve to scanning speed.
As seen from Figure 7, the square root of scanning speed is all had good linear relationship by oxidation peak current and reduction peak current, is wherein oxidation peak current by the curve being labeled with symbol " " and the subduplicate equation of linear regression of sweep speed is Ipk=9.789+19.816ν1/2, its linearly dependent coefficient r=0.987；Reduction peak current and the subduplicate equation of linear regression of sweep speed are Ipk=-36.692-20.818ν1/2, its linearly dependent coefficient r=0.991.Show that the Graphene chemically modified electrode that this example prepares has good electrochemical stability.(two curves of Fig. 7 please be described
Fig. 8 is the Graphene chemically modified electrode that embodiment one obtains, at 0.001MK3Fe(CN)6+0.001MK4Fe(CN)6The oxidoreduction spike potential difference in+1MKCl solution subduplicate curve to scanning speed.As seen from Figure 8, the square root of oxidoreduction spike potential difference and scanning speed has good linear relationship.Oxidoreduction spike potential difference is △ E=175.5+72.66 ν with the subduplicate equation of linear regression of sweep speed1/2, its linearly dependent coefficient r=0.992. shows that the Graphene chemically modified electrode that this example prepares has good electrochemical stability.
Embodiment two
The method of this example is essentially identical with the preparation method of embodiment one, the difference is that only:
The substrate adopted in A step is SiO2/ Si sheet.
The carbon-source gas adopted in B step is methane, and the volume ratio of methane and hydrogen is 1:1；The growth temperature of Graphene is 1200 DEG C；Growth time is 1min.
Embodiment three
The method of this example is essentially identical with the preparation method of embodiment one, is different in that:
The carbon-source gas adopted in B step is ethylene, and the volume ratio of ethylene and hydrogen is 1:50；The growth temperature of Graphene is 600 DEG C；Growth time is 180min.
Embodiment four
The method of this example is essentially identical with the preparation method of embodiment one, is different in that:
The carbon-source gas adopted in B step is methane with acetylene by the mixing gas of the volume ratio of 1:1, and the volume ratio of carbon-source gas and hydrogen is 1:100；The growth temperature of Graphene is 1000 DEG C；Growth time is 80min.
Embodiment five
The method of this example is essentially identical with the preparation method of embodiment one, is different in that:
The carbon-source gas adopted in B step is ethylene with acetylene by the mixing gas of the mass ratio of 2:1；The growth temperature of Graphene schedules 800 DEG C；Growth time is 1min.
Claims (4)
1. the method that growth in situ prepares Graphene chemically modified electrode, the steps include:
A, substrate cleaning
Substrate is sequentially placed into acetone, dehydrated alcohol and secondary deionized water ultrasonic cleaning, to remove greasy dirt and other impurity on its surface；Then, substrate is placed in air dry oven and dries, stand-by；Described substrate is quartz glass plate or SiO2/ Si sheet；
B, growth in situ Graphene
The substrate that A step obtains is placed in clean quartz boat, and quartz boat is placed in the quartz ampoule of horizontal resistance furnace；First logical argon removes the oxygen in quartz ampoule, then under the protection of argon, quartz ampoule is heated to the growth temperature of Graphene；Then it is incubated 1～180min, changes logical carbon-source gas and hydrogen when insulation；Subsequently, being cooled to room temperature under the protection of argon, namely taking-up obtains growth in situ the substrate of Graphene；
C, chemically modified electrode preparation
The substrate that the growth in situ that B step obtains has Graphene is connected upper conductor or is directly placed in fixture, obtains Graphene chemically modified electrode.
2. the method that a kind of growth in situ according to claim 1 prepares Graphene chemically modified electrode, it is characterised in that: one or more the mixture that carbon-source gas is acetylene, methane, ethylene, acetylene in described B step.
3. the method that a kind of growth in situ Graphene according to claim 1 prepares its chemically modified electrode, it is characterised in that: the growth temperature of the Graphene in described B step is 600～1200 DEG C.
4. the method that a kind of growth in situ Graphene according to claim 1 prepares its chemically modified electrode, it is characterised in that: carbon-source gas and the volume ratio of hydrogen in described B step are 1:1～100.
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| CN104609411A (en) * | 2015-02-05 | 2015-05-13 | 浙江大学 | Quartz boat for graphene growth |
| CN111665284A (en) * | 2019-03-08 | 2020-09-15 | 天津大学 | Application of doped graphene as sensing material |
| CN111517308B (en) * | 2020-04-01 | 2023-01-20 | 湖南二零八先进科技有限公司 | Novel laser gyroscope cathode for growing graphene based on surface CVD method |
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