CN107703195B - A kind of preparation method of graphene-metal organic frame composite material modified electrode - Google Patents
A kind of preparation method of graphene-metal organic frame composite material modified electrode Download PDFInfo
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Abstract
The present invention provides a kind of graphene-metal organic frame composite material modified electrode preparation methods, utilize electrode described in graphene modified, the electrode after modification is immersed in the solution obtained containing metal-organic framework material in advance again and is reacted, it washed, dried after taking-up, obtain the graphene-metal organic frame composite material modified electrode.Graphene-metal organic frame composite material modified electrode of the method for the present invention preparation has high surface area, bio-compatibility and shows electro-chemical activity in electrode surface, has a wide range of applications in the fields such as bio-sensing and electrochemical catalysis.
Description
Technical field
The present invention relates to functional material preparations and electrochemical technology field, in particular to a kind of graphene-metal machine frame
The preparation method of frame composite material modified electrode.
Background technique
In recent years, metal organic framework (Metal-organic framework, MOF) material is because it is with big ratio table
It face, periodically adjustable aperture and gets the attention the features such as the removable chemical property cut.MOF material generally has more
The topological structure of change, size, shape and the composition in hole etc. can be closed by selection different ligands and metal ion or change
It is adjusted at strategy.More importantly the functionality of skeleton is not limited only to the porosity of own, can also have benefited from certainly
The magnetism of body metal, the chirality of catalytic or ligand or fluorescence etc. can also originate from the synergistic effect of the two.Therefore,
MOF material provides possibility for the identification of molecule and sensing, thus in gas separation storage, catalysis, drug delivery and chemistry
Sensing etc. shows huge application potential.In Electroanalytical Chemistry field, researcher utilizes the catalytic performance of MOF material
With signal amplification design electrochemical sensor, realize substrate molecule Sensitive Determination [(a) Anal.Chem., 2015,
87,10635-10641；(b)Anal.Chem.,2015,87,11345.].
Although having carried out active and effective work, MOF is applied to the research in terms of electrochemica biological sensor
Still in the exploratory stage, various functional methods and effect are also lacked with the understanding of system.Copper-based MOF materials expectations should have very
Good electro-chemical activity, then how to make according to actual needs MOF material there is specific chemical property rather than by
In electroactive medium molecule, be expand its electrochemical biosensor field application range effective way [Anal.Chem.,
2016,88,12516.]。
Therefore being badly in need of finding a kind of has high surface area, bio-compatibility and to show outstanding electrochemistry in electrode surface living
The composite material and preparation method of property solves the above problems.
Summary of the invention
The technical problem to be solved by the present invention is to the problems for the electro-chemical activity difference of MOF material in the prior art, mention
A kind of preparation method of graphene-metal organic frame composite material modified electrode is supplied.
In order to solve the above technical problem, the present invention provides technical solution are as follows:
A kind of preparation method of graphene-metal machine frame composite material modified electrode, utilizes electricity described in graphene modified
Pole, then the electrode after modification is immersed in the solution obtained containing metal-organic framework material in advance and is reacted, it takes out
By washing, drying, the graphene-metal organic frame composite material modified electrode is obtained.
Electrode used in preparation method of the invention can be any appropriate electrode, but preferably, in the present invention
An embodiment in, above-mentioned electrode be carbon-based electrode and/or metal electrode.It is highly preferred that above-mentioned carbon electrode is glass carbon electricity
Pole, above-mentioned metal electrode are silver electrode or platinum electrode.
Preferably, graphene used in preparation method of the invention is carboxylated graphene.
The double surface-functionalized structures of carboxylated graphene can be used as structure directing agent and assemble for molecule, by upper and lower
The carboxyl and metal ion bidentate bridging on surface layer, thus the intensity of reinforced composite structure.Carboxylated graphene is led with structure
Double action to template and structural framing ligand, can with MOF is compound prepares the different crystalline material of pattern, be structure directing
The design of composite material provide the foundation.Preferred embodiment of the invention utilizes the structure-directing effect of carboxylated graphene,
The copper-based MOF material of glass-carbon electrode building nanometer flower pattern；Resulting graphene/MOF composite material has electro-chemical activity, thus
Promote application of the electro-chemical activity MOF material in terms of electrochemistry.
More specifically, in an embodiment of the invention, the above method can comprise the following steps that
Step 1) mixes the aqueous solution containing metal ion soluble-salt with the organic solution containing trimesic acid,
It is reacted 6~10 days under the conditions of 65~85 DEG C, obtains the solution containing metal-organic framework material；
The electrode is polished, is cleaned, is dry by step 2), and carboxylated graphene solution is applied to above-mentioned electricity after processing
Pole surface is dried, and the electrode of graphene modified is obtained；
The electrode of graphene modified obtained in step 2) is placed in organic containing metal obtained in step 1) by step 3)
It in the solution of frame material, is taken out after impregnating 1~10 day, it is multiple to obtain the graphene-metal organic frame after cleaned, dry
Condensation material modified electrode.
Preferably, the metal ion in step 1) can be for selected from copper ion, iron ion, cobalt ions, nickel ion or manganese
One or more of ion.
It is highly preferred that in an embodiment of the invention, the metal ion in step 1) is copper ion.
Preferably, in step 1) after the reaction was completed, the obtained solution containing metal-organic framework material is carried out
It filters.Can guarantee the coordination of metal ion Yu graphene surface layer carboxyl in this way, thus make subsequent crystal growth along
Specific direction carries out, and prepares nanometer flower pattern composite material.
Preferably, above-mentioned suction filtration uses diameter for 50mm, filter opening is that 0.45 μm of organic filter membrane is filtered, thus mistake
Filter out bulky grain metal-organic framework material.
Preferably, in an embodiment of the invention, metal ion soluble-salt and equal benzene three in step 1)
The molar ratio of formic acid is 0.5:1~2.5:1.It is highly preferred that the molar ratio of above-mentioned metal ion soluble-salt and trimesic acid
For 1.8:1.
Preferably, in an embodiment of the invention, the water-soluble of metal ion soluble-salt is contained in step 1)
The volume ratio of liquid and the organic solution containing trimesic acid is 0.5:1~1.5:1.It is highly preferred that above-mentioned volume ratio is
1:1.
Preferably, organic solution described in step 1) is alcoholic solution；It is highly preferred that above-mentioned alcoholic solution is ethanol solution.
Preferably, the reaction temperature in step 1) is 75 DEG C, the reaction time is 8 days.
Preferably, in an embodiment of the invention, the concentration of the carboxylated graphene solution in step 2) is
0.2mg/mL~0.4mg/mL.It is highly preferred that the concentration of above-mentioned carboxylated graphene solution is 0.2mg/mL.
Preferably, the time that the carboxylated graphene modified glass carbon plate in step 3) impregnates in filtrate is 7 days.
As a kind of preferred mode of the invention, preparation method of the present invention the following steps are included:
Step 1) is by 1~5mmol Gerhardite stirring and dissolving in 12mL H2In O；Secondly, by the equal benzene three of 2.0mmol
Formic acid ultrasonic agitation is scattered in 12mL dehydrated alcohol.Then, the two is mixed and is shaken up, pour into the reaction of 40mL stainless steel high temperature
In kettle, 65~85 DEG C are reacted 6~10 days；It is cooled to room temperature, the suspension of resulting copper-based MOF is filtered, bulky grain is filtered out
Copper-based MOF material, filtrate is divided into the equal portions of 5mL, and is placed in weighing bottle.
Step 2) polishes smooth the glass carbon plate of 10 × 10 × 3mm with 0.5 μm of alumina powder on polishing cloth, then divides
It is cleaned by ultrasonic 10 minutes not in acetone and pure water, is dried up with high pure nitrogen.Then, 10 μ L various concentrations are pipetted with liquid-transfering gun
Carboxylated graphene solution drop coating is dried in clean glass carbon plate surface, infrared lamp.
The glass carbon plate of carboxylated graphene modified obtained in step 2) is placed in the resulting filtrate of step 1) by step 3)
It impregnates 1~10 day and takes out, and rinsed with deionized water, naturally dry is to get nanometer flower pattern graphene/MOF composite material modification
Electrode.
There is provided a kind of graphene-metal organic frame composite material modified electrodes for another aspect of the present invention, should
Electrode is made by above-mentioned preparation method.
A nanometer flower shape can be shown under Electronic Speculum by composite material prepared by the above method.
There is provided a kind of above-mentioned graphene-metal organic frame composite material modified electrodes for another aspect of the present invention
Application, which can be applied to application of electrode in electrochemica biological sensor, electrochemical catalysis or hydrogen peroxide catalyzed.With
When hydrogen peroxide catalyzed, detection range can reach 0.2 μM~184.5 μM.
The invention has the benefit that
1) by being filtered to obtain its filtrate to the solution containing metal-organic framework material of preparation, it ensure that metal
The coordination of ion and graphene surface layer carboxyl, thus carry out the crystal growth of second step along specific direction, preparation
Nanometer flower pattern composite material；
2) synthesis technology is simple, and cost is relatively low, can react and be stabilized at room temperature, and repeatability is strong；
3) nano flower-like graphene/MOF composite material of the present invention has high surface area, bio-compatibility and in electrode surface
Show electro-chemical activity；
4) nano flower-like graphene/MOF composite material modification electrode has in the fields such as bio-sensing and electrochemical catalysis
Broad application prospect.
Detailed description of the invention
Fig. 1 is the scanning electron of the different enlargement ratios of graphene/MOF composite material modified electrode made from embodiment 1
Microscope figure, wherein left figure is 2000 times of amplification, and right figure is 10000 times of amplification；
Fig. 2 is graphene/MOF composite material modified electrode scanning electron microscope/elemental analysis made from embodiment 1
Figure, wherein left figure be amplification 10000 times, right figure be amplification 10000 times；
Fig. 3 is graphene/MOF composite material modified electrode x-ray photoelectron spectroscopy figure made from embodiment 1；
Fig. 4 is graphene/MOF composite material modified electrode X ray diffracting spectrum made from embodiment 1；
Fig. 5 divides for scanning electron microscope/element of graphene/MOF composite material modified electrode obtained in comparative example
The figure of analysis, wherein A is graphene/MOF composite material modified electrode made from comparative example 1, and B is graphite made from comparative example 2
Alkene/MOF composite material modified electrode；
Fig. 6 is graphene/MOF composite material modified electrode made from embodiment 1 and comparative example 1 in 0.1M phosphate-buffered
Electrochemistry cyclic voltammetry curve figure in solution；
Fig. 7 is the chrono-amperometric song that graphene made from embodiment 1/MOF composite material modified electrode detects hydrogen peroxide
The relationship of line chart and steady-state current and concentration of hydrogen peroxide schemes B wherein figure A is the chronoa mperometric plot figure for detecting hydrogen peroxide
For the relational graph of steady-state current and concentration of hydrogen peroxide.
Specific embodiment
The invention discloses a kind of graphene-metal organic frame composite material modified electrode preparation method, this fields
Technical staff can use for reference present disclosure, be suitably modified realization of process parameters.It is important to note that all similar replacements
Apparent to those skilled in the art with changing, they are considered as being included in the present invention, and related personnel
Obviously content described herein can be modified or be suitably changed on the basis of not departing from the content of present invention, spirit and scope with
Combination, carrys out implementation and application the technology of the present invention.
In the present invention, unless otherwise stated, Science and Technology noun used herein has art technology
The normally understood meaning of personnel institute.
It is right combined with specific embodiments below in order to make those skilled in the art more fully understand technical solution of the present invention
The present invention is described in further detail.
The preparation of 1 graphene of embodiment/MOF composite material modified electrode
Firstly, by 3.6mmol Gerhardite stirring and dissolving in 12mL H2In O；Secondly, by the equal benzene front three of 2.0mmol
Acid ultrasonic agitation is scattered in 12mL dehydrated alcohol.Then, the two is mixed and is shaken up, pour into 40mL stainless steel high temperature reaction kettle
In, 75 DEG C are reacted 8 days；It is cooled to room temperature, the suspension of resulting copper-based MOF is filtered, the copper-based MOF material of bulky grain is filtered out
Material, filtrate is divided into the equal portions of 5mL, and is placed in weighing bottle.
Then, the glass carbon plate of 10 × 10 × 3mm is polished smooth on polishing cloth with 0.5 μm of alumina powder, is then divided
It is cleaned by ultrasonic 10 minutes not in acetone and pure water, is dried up with high pure nitrogen.Then, 10 μ L 0.2mg/mL are pipetted with liquid-transfering gun
Carboxylated graphene solution drop coating in clean glass carbon plate surface, infrared lamp is dried.
It takes out, and spends finally, the glass carbon plate of carboxylated graphene modified is placed in resulting filtrate and is impregnated 7 days
Ionized water rinses, and naturally dry is to get nanometer flower pattern graphene/MOF composite material modification electrode.
The preparation of 2 graphenes of embodiment/MOF composite material modified electrode
Firstly, by 1mmol Gerhardite stirring and dissolving in 6mL H2In O；Secondly, by 2.0mmol trimesic acid
Ultrasonic agitation is scattered in 12mL dehydrated alcohol.Then, the two is mixed and is shaken up, pour into 40mL stainless steel high temperature reaction kettle
In, 65 DEG C are reacted 10 days；It is cooled to room temperature, the suspension of resulting copper-based MOF is filtered, the copper-based MOF of bulky grain is filtered out
Material, filtrate are divided into the equal portions of 5mL, and are placed in weighing bottle.
Then, the glass carbon plate of 10 × 10 × 3mm is polished smooth on polishing cloth with 0.5 μm of alumina powder, is then divided
It is cleaned by ultrasonic 10 minutes not in acetone and pure water, is dried up with high pure nitrogen.Then, pipette 10 μ L0.4mg/mL's with liquid-transfering gun
Carboxylated graphene solution drop coating is dried in clean glass carbon plate surface, infrared lamp.
It takes out, is used in combination finally, the glass carbon plate of carboxylated graphene modified is placed in resulting filtrate and is impregnated 10 days
Deionized water is rinsed, and naturally dry is to get nanometer flower pattern graphene/MOF composite material modification electrode.
The preparation of 3 graphenes of embodiment/MOF composite material modified electrode
Firstly, by 5mmol Gerhardite stirring and dissolving in 18mLH2In O；Secondly, by 2.0mmol trimesic acid
Ultrasonic agitation is scattered in 12mL dehydrated alcohol.Then, the two is mixed and is shaken up, pour into 40mL stainless steel high temperature reaction kettle
In, 85 DEG C are reacted 6 days；It is cooled to room temperature, the suspension of resulting copper-based MOF is filtered, the copper-based MOF material of bulky grain is filtered out
Material, filtrate is divided into the equal portions of 5mL, and is placed in weighing bottle.
Then, the glass carbon plate of 10 × 10 × 3mm is polished smooth on polishing cloth with 0.5 μm of alumina powder, is then divided
It is cleaned by ultrasonic 10 minutes not in acetone and pure water, is dried up with high pure nitrogen.Then, pipette 10 μ L0.3mg/mL's with liquid-transfering gun
Carboxylated graphene solution drop coating is dried in clean glass carbon plate surface, infrared lamp.
It takes out, and spends finally, the glass carbon plate of carboxylated graphene modified is placed in resulting filtrate and is impregnated 1 day
Ionized water rinses, and naturally dry is to get nanometer flower pattern graphene/MOF composite material modification electrode.
The preparation of 4 graphenes of embodiment/MOF composite material modified electrode
Firstly, by 5mmol Gerhardite stirring and dissolving in 18mL H2In O；Secondly, by 2.0mmol trimesic acid
Ultrasonic agitation is scattered in 12mL dehydrated alcohol.Then, the two is mixed and is shaken up, pour into 40mL stainless steel high temperature reaction kettle
In, 85 DEG C are reacted 6 days；It is cooled to room temperature, the suspension of resulting copper-based MOF is filtered, the copper-based MOF material of bulky grain is filtered out
Material, filtrate is divided into the equal portions of 5mL, and is placed in weighing bottle.
Then, the glass carbon plate of 10 × 10 × 3mm is polished smooth on polishing cloth with 0.5 μm of alumina powder, is then divided
It is cleaned by ultrasonic 10 minutes not in acetone and pure water, is dried up with high pure nitrogen.Then, 10 μ L 0.3mg/mL are pipetted with liquid-transfering gun
Carboxylated graphene solution drop coating in clean glass carbon plate surface, infrared lamp is dried.
It takes out, and spends finally, the glass carbon plate of carboxylated graphene modified is placed in resulting filtrate and is impregnated 1 day
Ionized water rinses, and naturally dry is to get nanometer flower pattern graphene/MOF composite material modification electrode.
1 conventional method of comparative example prepares MOF composite material modified electrode
Firstly, by 3.6mmol Gerhardite stirring and dissolving in 12mL H2O；Secondly, by 2.0mmol trimesic acid
Ultrasonic agitation is scattered in 12mL dehydrated alcohol.Then, the two is mixed and is shaken up, poured into 40mL stainless steel high temperature reaction kettle,
75 DEG C are reacted 8 days；The suspension of resulting copper-based MOF is filtered, filtrate is divided into the equal portions of 5mL, and is placed in weighing bottle.
Then, the glass carbon plate of 10 × 10 × 3mm is polished smooth on polishing cloth with 0.5 μm of alumina powder, is then divided
It is cleaned by ultrasonic 10 minutes not in acetone and pure water, is dried up with high pure nitrogen.
It is taken out finally, clean naked glass carbon plate is placed on to impregnate 7 days in gained filtrate, deionized water is rinsed, natural
It dries, is scanned the characterization of electron microscope.
2 carboxylated graphene modified of comparative example is to the influence of graphene/MOF composite material modified electrode
Firstly, by 3.6mmol Gerhardite stirring and dissolving in 12mL H2O；Secondly, by 2.0mmol trimesic acid
Ultrasonic agitation is scattered in 12mL dehydrated alcohol.Then, the two is mixed and is shaken up, poured into 40mL stainless steel high temperature reaction kettle,
75 DEG C are reacted 8 days；The suspension of resulting copper-based MOF is filtered, filters out the copper-based MOF material of bulky grain, filtrate is divided into 5mL
Equal portions, and be placed in weighing bottle.
Then, the glass carbon plate of 10 × 10 × 3mm is polished smooth on polishing cloth with 0.5 μm of alumina powder, is then divided
It is cleaned by ultrasonic 10 minutes not in acetone and pure water, is dried up with high pure nitrogen.10 μ L 0.2mgmL are pipetted with liquid-transfering gun-1Oxygen
Graphite alkene drop coating is dried in glass carbon plate surface, infrared lamp；
It is taken out finally, the glass carbon plate that graphene oxide is modified is placed in resulting filtrate and is impregnated 7 days, deionized water
It rinses, naturally dry is scanned the characterization of electron microscope.
Experimental result:
As shown in Figure 1-3, the compound pattern for making material of the graphene/MOF prepared in embodiment largely occurs
Change, Scanning Electron microscope photo shows that composite material is flower-shaped substantially, and Cu Elemental redistribution is uniform.
Fig. 4 demonstrate graphene/MOF it is compound make material glassy carbon electrode surface crystalline structure based on 220 crystal faces.
It can be seen that the graphene/MOF composite material modification electricity prepared in comparative example 1 and comparative example 2 from the A and B of Fig. 5
Generation of the pole without nanometer flower pattern MOF composite material, it was demonstrated that carboxylated graphene plays the important of structure directing agent to crystal morphology
Effect.
1 graphene of experimental example/MOF composite material modified electrode surface electrochemistry determination of activity
Utilize method preparation nanometer flower pattern graphene/MOF composite material modification electrode in embodiment 1.Modification electricity
The electro-chemical activity measurement of pole carries out on electrochemical workstation CHI 660D.The work station uses traditional three-electrode system:
Graphene/MOF composite material modified electrode is as working electrode, and Ag/AgCl electrode is as reference electrode, platinum electrode conduct pair
Electrode.Cyclic voltammetry scan is carried out in 0.1M phosphate buffer solution (pH=7.0) to the modified electrode, as a result such as Fig. 6
It is shown.
The MOF composite material modified electrode surface electrochemistry determination of activity that comparative example 3 is prepared using the method for comparative example 1
Graphene/MOF composite material modification electrode is prepared using the method in comparative example 1.Using identical as experimental example 1
The method of inspection, that is, cyclic voltammetry.The electro-chemical activity measurement of the modified electrode is enterprising in electrochemical workstation CHI 660D
Row.The work station uses traditional three-electrode system: graphene/MOF composite material modified electrode is as working electrode, Ag/
AgCl electrode is used as reference electrode, platinum electrode to electrode.To the modified electrode in 0.1M phosphate buffer solution (pH
=7.0) cyclic voltammetry scan is carried out in, as a result as shown in Figure 6.
Experimental result:
In Fig. 6, the result curve of experimental example 1 shows a pair of of redox peaks occur in -0.1V and -0.3V or so, this
It is attributed to copper ion in graphene/MOF composite material and shows copper-based-metal organic frame material in the redox of electrode surface
Material has been grown in the glassy carbon electrode surface of carboxylated graphene modified really.
In Fig. 6, the result curve of comparative example 3 shows graphene/MOF composite material modified electrode prepared by experimental example 1
Redox peak current it is more significant, the slightly negative shifting of spike potential, illustrate electronics its surface delivery rate faster.Result above
Illustrate, graphene/MOF composite material modified electrode surface electrochemistry activity of the method for the present invention preparation is much better than comparative example 1
Method prepare the electrode of graphene/MOF composite material modification.
Catalytic activity of 2 graphenes of the experimental example/MOF composite material modified electrode to hydrogen peroxide
Utilize method preparation nanometer flower pattern graphene/MOF composite material modification electrode in embodiment 1.Modification electricity
The electro-chemical activity measurement of pole carries out on electrochemical workstation CHI 660D.The work station uses traditional three-electrode system:
Graphene/MOF composite material modified electrode is as working electrode, and Ag/AgCl electrode is as reference electrode, platinum electrode conduct pair
Electrode.By graphene obtained in above-described embodiment 1/MOF composite material modified electrode pH=7.0 0.1M phosphate-buffered
(different amounts of H is continuously added in solution2O2) I-t curved scanning is carried out, successively detect its curent change, acquired results such as Fig. 7 institute
Show, linear equation is I=0.79161C+0.39262 (R=0.998), and detection range is 0.2 μM~184.5 μM, minimum inspection
Rising limit is 67nM.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (14)
1. a kind of graphene-metal organic frame composite material modified electrode preparation method, which is characterized in that utilize graphene
The electrode is modified, then the electrode after modification is immersed in the solution obtained containing metal-organic framework material in advance and is carried out
Reaction, is washed after taking-up, is dried, obtain the graphene-metal organic frame composite material modified electrode；
The preparation method comprises the following steps:
Step 1) mixes the aqueous solution containing metal ion soluble-salt with the organic solution containing trimesic acid, 65~
It is reacted 6~10 days under the conditions of 85 DEG C, obtains the solution containing metal-organic framework material；
The electrode is polished, is cleaned, is dry by step 2), and carboxylated graphene solution is applied to above-mentioned electrode table after processing
Face is dried, and the electrode of graphene modified is obtained；
The electrode of graphene modified obtained in step 2) is placed in by step 3) contains metal organic frame obtained in step 1)
It in the solution of material, is taken out after impregnating 1~10 day, obtains the graphene-metal organic frame composite wood after cleaned, dry
Expect modified electrode.
2. preparation method according to claim 1, which is characterized in that the graphene is carboxylated graphene, the electricity
Extremely carbon-based electrode and/or metal electrode.
3. preparation method according to claim 2, which is characterized in that the carbon electrode is glass-carbon electrode, the metal electricity
Extremely silver electrode or platinum electrode.
4. preparation method according to claim 1, which is characterized in that the step 1) metal ion be selected from copper ion,
One or more of iron ion, cobalt ions, nickel ion or manganese ion.
5. the preparation method according to claim 4, which is characterized in that the metal ion is copper ion.
6. preparation method according to claim 1, which is characterized in that after the step 1) reaction, will obtain containing gold
The solution for belonging to organic framework materials is filtered.
7. preparation method according to claim 1, which is characterized in that step 1) the metal ion soluble-salt and equal benzene
The molar ratio of tricarboxylic acid is 0.5:1~2.5:1.
8. preparation method according to claim 7, which is characterized in that step 1) the metal ion soluble-salt and equal benzene
The molar ratio of tricarboxylic acid is 1.8:1.
9. preparation method according to claim 1, which is characterized in that step 1) is described to contain metal ion soluble-salt
The volume ratio of aqueous solution and the organic solution containing trimesic acid is 0.5~1.5:1.
10. preparation method according to claim 9, which is characterized in that step 1) is described to contain metal ion soluble-salt
Aqueous solution and the organic solution containing trimesic acid volume ratio be 1:1.
11. preparation method according to claim 1, which is characterized in that step 2) the carboxylated graphene solution it is dense
Degree is 0.2mg/mL~0.4mg/mL.
12. preparation method according to claim 11, which is characterized in that step 2) the carboxylated graphene solution it is dense
Degree is 0.2mg/mL.
13. a kind of graphene-metal organic frame composite material modified electrode, which is characterized in that the electrode is by claim
Preparation method described in 1-12 any one is made.
14. a kind of application of graphene as claimed in claim 13-metal organic frame composite material modified electrode, feature
It is, the application of electrode is in electrochemica biological sensor, electrochemical catalysis or hydrogen peroxide catalyzed.
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