CN110412096A - Graphene oxide@ZIF-8 composite material modified electrode of reduction and preparation method thereof and detection application - Google Patents
Graphene oxide@ZIF-8 composite material modified electrode of reduction and preparation method thereof and detection application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 25
- 230000009467 reduction Effects 0.000 title claims abstract description 22
- 238000001514 detection method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims description 27
- 229920001817 Agar Polymers 0.000 claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000004780 naphthols Chemical class 0.000 claims abstract description 10
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 52
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 50
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 229950011260 betanaphthol Drugs 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 239000008272 agar Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001879 gelation Methods 0.000 claims description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000017 hydrogel Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000499 gel Substances 0.000 claims description 4
- 238000012417 linear regression Methods 0.000 claims description 4
- 239000008363 phosphate buffer Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- 241001481789 Rupicapra Species 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000010985 leather Substances 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003115 supporting electrolyte Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000001903 differential pulse voltammetry Methods 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 abstract description 31
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 abstract description 30
- 230000008901 benefit Effects 0.000 abstract description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VMYREBYTVVSDDK-FQEVSTJZSA-N (3s)-3-(naphthalen-2-ylsulfonylamino)-4-oxo-4-(2-phenylethylamino)butanoic acid Chemical compound O=C([C@@H](NS(=O)(=O)C=1C=C2C=CC=CC2=CC=1)CC(=O)O)NCCC1=CC=CC=C1 VMYREBYTVVSDDK-FQEVSTJZSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- -1 ZIF-8 compound Chemical class 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000083 pulse voltammetry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses complex film modified electrodes of oxide graphene@ZIF-8 of a kind of reduction and preparation method thereof and the application for detecting naphthol isomers simultaneously.2-methylimidazole solution is added in the reaction tube containing graphene oxide agar gel matrix, oxide graphene@ZIF-8 nano-complex is prepared using natural diffuseness osmosis, the oxide graphene@ZIF-8 nano-complex of thermal reduction preparation reduction after sample is divided into three layers by diffusion depth, and prepare corresponding modified electrode.Gained modified electrode of the invention has the characteristics that effective area is big, active site is more, good dispersion, the shortcomings that oxide graphene and ZIF-8 of reduction compensate for each other, the synergistic effect that the two has been played in terms of improving Direct Electrochemistry and electrocatalysis characteristic, improves the electric conductivity and catalytic performance of modified electrode.Gained modified electrode is realized to the highly sensitive of naphthol isomers while being detected, and has many advantages, such as that detection limit is low, detection range is wide, response quickly.
Description
Technical field:
The present invention relates to a kind of complex film modified electrodes of graphene oxide@ZIF-8 of reduction；It is repaired the invention further relates to described
Adorn the preparation method of electrode and its application in electrochemical sensing context of detection.
Background technique:
Naphthols is a kind of important Organic Chemicals and dyestuff intermediate in Chemical Manufacture in today's society, is there is engine dyeing
There is extensive application in material, organic pigment, pesticide and medicine.Naphthols has 2 kinds of isomers, i.e. alpha-Naphthol and betanaphthol.By
It often co-exists in environmental system, and has at low concentrations compared with high toxicity, therefore it is good, sensitive to establish a kind of stability in the two
It is particularly important to spend high detection method.Currently, the method for detecting the substance mainly has high performance liquid chromatography, gas-chromatography
Method, spectrophotometry, fluorescence method, Electrochemiluminescince etc., however these methods are since there are operating condition complexity, time-consuming, spirits
The disadvantages such as sensitivity is low, to limit it in the application of detection naphthol isomers.Electrochemical method has response quickly, sensitivity
The advantages that height, selectivity is good, at low cost, easy to operate, time saving, provides ideal selection for the detection of two kinds of isomers, but
Since oxidation spike potential of two kinds of isomers on commercial bare electrode is too close to, it is difficult to realize to the same of two kinds of isomeric compounds
When detect, therefore looking for a kind of suitable nano-complex as electrode modified material is improve its sensitivity and stability effective
Method.
Zeolite imidazole skeleton (ZIF) is that one kind of metal organic frame (MOFs) has compared with other most of MOFs
Be readily synthesized, thermal stability and the advantages that chemical stability, gas storage, separation, chemical sensitisation and in terms of show
Huge potentiality out.But ZIF is easy to be gathered into bulk and lead to lose cavernous structure, greatly reduces its electrochemical catalysis
Energy.If suitable template is selected to prepare ZIF using extensional mode as bracket and directed agents, it is avoided that ZIF assembles, guarantees it
Excellent electrochemical catalysis performance.
For GO as one of carbon material, the electric conductivity and chemical property of itself are all very good, are that one kind is used to prepare electrochemistry
The improvement material of sensor or biosensor.But the application performance of GO is limited, because the material can be by strong
Mutual sedimentation aggregation, or even accumulation forms graphite again, in order to improve the electrochemical catalysis performance of GO, researcher would generally
Be reduced into the graphene oxide (RGO) of reduction, can also by with other materials is compound improves its specific surface area, sufficiently
Its catalytic site of exposure.
Intend in the agar gel matrix containing GO to solve existing defect, the present invention when the above material is used alone
The method permeated using natural diffuseness, the multi ANN GO ZIF-8 in situ in reaction tube, then prepared by thermal reduction method
RGO@ZIF-8 nano-complex prepares corresponding modified electrode using the compound and examines while being used for naphthol isomers
It surveys.Using using natural diffuseness osmosis and thermal reduction preparation RGO@ZIF-8, can not only controllable preparation uniform particle diameter ZIF-8
Particle, and RGO nanometer sheet and the big specific surface area of ZIF-8, the original position on the surface RGO of especially ZIF-8 can also be made full use of
Growth effectively inhibits the rendezvous problem of the two, has given full play to the advantage of RGO nanometer sheet and ZIF-8 in terms of electrode modification,
Compensate for defect when they are used alone.RGO ZIF-8 compound is used for modified glassy carbon electrode, which can be with
More active sites, higher electric conductivity and good dispersibility are provided, the synergistic effect of two kinds of components is given full play to, thus
Direct Electrochemistry and electrocatalysis characteristic of the tested substance on modified electrode are improved, to establishing novel high-sensitivity Electrochemical Detection
Method is of great significance.
Summary of the invention:
In view of the deficiencies of the prior art and the demand of this field research and application, an object of the present invention are to provide one
The complex film modified electrode of graphene oxide@ZIF-8 of kind reduction, it is characterised in that the basal electrode of the modified electrode is glass carbon
Electrode, decorative material are the graphene oxide@ZIF-8 composite membrane of reduction；The graphene oxide@ZIF-8 composite wood of the reduction
Material is being used obtained by natural diffuseness osmosis and the preparation of thermal reduction method in the gel-type vehicle containing graphene oxide；It is described
Graphene oxide is denoted as GO；The graphene oxide of the reduction is denoted as RGO；The glass-carbon electrode is denoted as GCE；
The second object of the present invention is to be to provide a kind of preparation method of the complex film modified electrode of RGO@ZIF-8, feature
It is, comprising the following specific steps
(a) preparation of RGO@ZIF-8
The aqueous dispersions for using ultrasonic dispersion that graphene oxide GO is configured to concentration as 1mg/mL, pipette 20~40mL
Above-mentioned GO aqueous dispersions weigh 0.595g zinc nitrate and are dissolved in wherein into beaker, and adding a certain amount of agar powder makes its final matter
Measuring concentration is 0.5%, until agar powder is completely dissolved, addition 30mL n,N-Dimethylformamide continues to stir heating stirring
30min pipettes the above-mentioned mixed solution of certain volume into the cylindrical plastic pipe of 12mm × 100mm while hot, reaches described
2/3rds of plastic tube height do 6 plastic tubes in parallel, stand reaction 2h, agar after being sealed later with sealed membrane at room temperature
The gel of grey black is obtained after complete gelation；It weighs 3.284g 2-methylimidazole and is dissolved in the water and N that volume ratio is 1:1,
Dinethylformamide in the mixed solvent, after stirring and dissolving is complete, 6 plastic tubes for being slowly injected into above-mentioned gelation are remained
Remaining one third space stands 2 days after sealed membrane sealing and brings it about scattering and permeating reaction, obtains the hydrogel of grey black；
It is cut from edge 6 plastic tubes, the grey black jello in pipe is cut into three sections by the length of 5mm from top to bottom, then will put down
Three sections of the upper, middle and lower of row pipe is enriched with respectively, with the agar in n,N-Dimethylformamide dissolution jello, distinguishes after centrifugation
Collect three sections of upper, middle and lower of infusible precipitate；Again by three 150 DEG C of grey black deposit sample dry 2h, three kinds of black are obtained
RGO@ZIF-8 composite material；
(b) preparation of the complex film modified GCE of RGO@ZIF-8
Basal electrode sanding and polishing is cleaned by ultrasonic at mirror surface, then with ultrapure water, must be handled well after natural drying at room temperature
GCE；It disperses the RGO@ZIF-8 compound material ultrasound that step (a) is prepared in deionized water, being prepared into concentration is 1mg/
The dispersion liquid of mL takes 2~20 μ L dispersant liquid drops to be coated in the surface GCE handled well, up to RGO@ZIF-8 after natural drying at room temperature
Complex film modified GCE.
It is characterized in that, the particle diameter distribution of middle layer is most uniform in step (a) tri- samples of resulting RGO@ZIF-8, grain
Diameter is 30-80nm；In step (b), the polishing of the basal electrode is on chamois leather, using the alumina powder of partial size from big to small
End is successively polished, and the time of ultrasonic cleaning is 30s.
The three of the object of the invention are to provide a kind of complex film modified electrode of RGO ZIF-8 answering in detection naphthol isomers
With.Detection method are as follows: using the phosphate buffer of 0.1mol/L pH 7.5 as supporting electrolyte, different amounts of α-naphthalene will be contained
Phenol and betanaphthol are single or both mixed electrolyte solution is added in electrolytic cell, using modified electrode as working electrode, uses difference
Pulse voltammetry detection, respectively obtains the oxidation peak current of alpha-Naphthol and betanaphthol and the equation of linear regression of its concentration, uses
Same method measures the oxidation peak current of alpha-Naphthol and betanaphthol in sample to be tested, substitutes into equation of linear regression to get to test sample
The content of alpha-Naphthol and betanaphthol in product.
Compared with prior art, the present invention having the following beneficial effects:
(a) RGO@ZIF-8 composite material of the present invention is directly to contain GO using the method for natural diffuseness infiltration
Agar gel matrix in multi ANN ZIF-8, then be prepared by thermal reduction method, obtained composite material partial size is equal
One, preparation method is simple；
(b) the RGO@ZIF-8 composite material modified electrode played in terms of electro-catalysis alpha-Naphthol and betanaphthol RGO and
The synergistic effect of ZIF-8: thermal reduction gained RGO improves the electric conductivity of composite membrane；ZIF-8 natural diffuseness in gel-type vehicle seeps
Saturating growth in situ not only ensure that being uniformly distributed for partial size, but also prevent the aggregation of RGO, increase composite material active site and
Specific surface area improves absorption and capture ability of the modified electrode to detected material；
(c) the complex film modified electrode of RGO@ZIF-8 context of detection while to alpha-Naphthol and betanaphthol obtains
The wider range of linearity (8nM~100nM) and lower detection limit (alpha-Naphthol 2.7nM, betanaphthol 2.6nM), and the oxygen of the two
Change peak to be clearly separated, therefore can be very good to realize detection while to naphthol isomers, detection method stability is good, sensitivity
It is high.
Detailed description of the invention:
A in Fig. 1, B, C are respectively 1,2, No. 3 samples of RGO@ZIF-8 composite material that step (a) is prepared in embodiment 1
The SEM of product schemes.
Fig. 2 is comparative example 1, comparative example 2, GCE (a), ZIF-8/GCE (b), GO@corresponding to comparative example 3 and embodiment 1
The 5.0mmol/L Fe (CN) of ZIF-8/GCE (c) and RGO@ZIF-8/GCE (d) potassium chloride containing 0.1mol/L6 3-/4-(1:1) solution
In electrochemical impedance figure.
Fig. 3 is embodiment 1, comparative example 4 and the corresponding RGO@ZIF-8/GCE (b) of comparative example 5, RGO@ZIF-8-1/GCE
(a) and RGO@ZIF-8-3/GCE (c) is the 0.1mol/L pH's 7.5 containing 0.1mmol/L alpha-Naphthol and betanaphthol mixed liquor
Cyclic voltammogram in phosphate buffer.
On RGO@ZIF-8/GCE (a), under RGO@ZIF-8/GCE (b) and RGO@ZIF-8 in/GCE (c) containing 0.1mmol/
CV figure in the PBS (pH=7.5) of L alpha-Naphthol and 0.1mmol/L betanaphthol
Fig. 4 is 1 gained RGO ZIF-8/GCE of embodiment pH is 7.5, to sweep speed be 100mV/s, fixed betanaphthol concentration is
The DPV curve of (a-h:8,10,20,30,50,70,90,100nmol/L) when being gradually increased when 40nmol/L with alpha-Naphthol concentration；
Linear relationship chart of the illustration between peak current and concentration.
Fig. 5 is 1 gained RGO@ZIF-8/GCE of embodiment pH is 7.5, to sweep speed be 100mV/s, fixed alpha-Naphthol concentration is
The DPV curve of (a-h:8,10,20,30,50,70,90,100nmol/L) when being gradually increased when 40nmol/L with betanaphthol concentration；
Linear relationship chart of the illustration between peak current and concentration.
Specific embodiment:
To further understand the present invention, present invention will be further explained below with reference to the attached drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1:
(a) preparation of RGO@ZIF-8
The aqueous dispersions for using ultrasonic dispersion that graphene oxide GO is configured to concentration as 1mg/mL, it is above-mentioned to pipette 20mL
GO aqueous dispersions weigh 0.595g zinc nitrate and are dissolved in wherein into beaker, and adding a certain amount of agar powder keeps its final mass dense
Degree is 0.5%, until agar powder is completely dissolved, addition 30mL n,N-Dimethylformamide continues to stir 30min heating stirring,
The above-mentioned mixed solution of certain volume is pipetted while hot into the cylindrical plastic pipe of 12mm × 100mm, reaches the plastic tube
2/3rds of height do 6 plastic tubes in parallel, stand reaction 2h after being sealed later with sealed membrane at room temperature, and agar is completely solidifying
The gel of grey black is obtained after gelatinization；It weighs 3.284g 2-methylimidazole and is dissolved in the water and N that volume ratio is 1:1, N- diformazan
Base formamide in the mixed solvent after stirring and dissolving is complete, is slowly injected into 6 plastic tubes remaining three of above-mentioned gelation
/ mono- space stands 2 days after sealed membrane sealing and brings it about scattering and permeating reaction, obtains the hydrogel of grey black；From edge
6 plastic tubes are cut, the grey black jello in pipe is cut into three sections by the length of 5mm from top to bottom, then by parallel pipe
Three sections of upper, middle and lower is enriched with respectively, with the agar in n,N-Dimethylformamide dissolution jello, collects respectively after centrifugation
In lower three sections of infusible precipitate；Again by three 150 DEG C of grey black deposit sample dry 2h, the RGO@ZIF- of three kinds of black is obtained
8 composite materials, number is 1 from top to bottom, and 2,3 is spare；
(b) preparation of the complex film modified GCE of RGO@ZIF-8
Basal electrode sanding and polishing is cleaned by ultrasonic at mirror surface, then with ultrapure water, must be handled well after natural drying at room temperature
GCE；It disperses RGO@ZIF-8 No. 2 sample ultrasonics of composite material that step (a) is prepared in deionized water, is prepared into dense
Degree is the dispersion liquid of 1mg/mL, and the 7 μ L dispersant liquid drops is taken to be coated in the surface GCE handled well, up to RGO@after natural drying at room temperature
The complex film modified GCE of ZIF-8.
Embodiment 2:
(a) preparation of RGO@ZIF-8
It is only 30mL by the stereomutation that pipettes of GO aqueous dispersions according to operation sequence in step (a) in embodiment 1,
Its preparation method is identical with condition；
(b) preparation of the complex film modified GCE of RGO@ZIF-8
According to operation sequence in step (b) in embodiment 1, the RGO@ZIF-8 composite material 2 that step (a) is prepared
Number sample ultrasonic is scattered in deionized water, is prepared into the dispersion liquid that concentration is 1mg/mL, and the 7 μ L dispersant liquid drops is taken to be coated in processing
The good surface GCE, up to the complex film modified GCE of RGO@ZIF-8 after natural drying at room temperature.
Embodiment 3:
(a) preparation of RGO@ZIF-8
According to the method and condition preparation of step (a) in embodiment 1；
(b) preparation of the complex film modified GCE of RGO@ZIF-8
Basal electrode sanding and polishing is cleaned by ultrasonic at mirror surface, then with ultrapure water, must be handled well after natural drying at room temperature
GCE；It disperses RGO@ZIF-8 No. 2 sample ultrasonics of composite material that step (a) is prepared in deionized water, is prepared into dense
Degree is the dispersion liquid of 1mg/mL, and the 5 μ L dispersant liquid drops is taken to be coated in the surface GCE handled well, up to RGO@after natural drying at room temperature
The complex film modified GCE of ZIF-8.
Embodiment 4:
(a) preparation of RGO@ZIF-8
According to the method and condition preparation of step (a) in embodiment 1；
(b) preparation of the complex film modified GCE of RGO@ZIF-8
Basal electrode sanding and polishing is cleaned by ultrasonic at mirror surface, then with ultrapure water, must be handled well after natural drying at room temperature
GCE；It disperses RGO@ZIF-8 No. 2 sample ultrasonics of composite material that step (a) is prepared in deionized water, is prepared into dense
Degree is the dispersion liquid of 1mg/mL, and the 9 μ L dispersant liquid drops is taken to be coated in the surface GCE handled well, up to RGO@after natural drying at room temperature
The complex film modified GCE of ZIF-8.
Embodiment 5:
(a) preparation of RGO@ZIF-8
According to the method and condition preparation of step (a) in embodiment 1；
(b) preparation of the complex film modified GCE of RGO@ZIF-8
Basal electrode sanding and polishing is cleaned by ultrasonic at mirror surface, then with ultrapure water, must be handled well after natural drying at room temperature
GCE；It disperses RGO@ZIF-8 No. 2 sample ultrasonics of composite material that step (a) is prepared in deionized water, is prepared into dense
Degree is the dispersion liquid of 1mg/mL, and the 12 μ L dispersant liquid drops is taken to be coated in the surface GCE handled well, up to RGO@after natural drying at room temperature
The complex film modified GCE of ZIF-8.
Comparative example 1:
Directly with naked GCE.
Comparative example 2:
(a) preparation of ZIF-8
It weighs 0.595g zinc nitrate to be dissolved in the beaker of 20mL deionized water, adding a certain amount of agar powder makes its final matter
Measuring concentration is 0.5%, until agar powder is completely dissolved, addition 30mL n,N-Dimethylformamide continues to stir heating stirring
30min pipettes the above-mentioned mixed solution of certain volume into the cylindrical plastic pipe of 12mm × 100mm while hot, reaches described
2/3rds of plastic tube height do 6 plastic tubes in parallel, stand reaction 2h, agar after being sealed later with sealed membrane at room temperature
It is spare after complete gelation；It weighs 3.284g2- methylimidazole and is dissolved in the water and N that volume ratio is 1:1, N- dimethyl formyl
Amine in the mixed solvent after stirring and dissolving is complete, is slowly injected into 6 remaining one thirds of plastic tube of above-mentioned gelation
Space stands 2 days after sealed membrane sealing and brings it about scattering and permeating reaction, obtains the hydrogel containing precipitating；From edge 6
Plastic tube is cut, and the jello in pipe is cut into three sections by the length of 5mm from top to bottom, then by three sections points of upper, middle and lower of parallel pipe
It Fu Ji not get up, with the agar in n,N-Dimethylformamide dissolution jello, collect three sections of upper, middle and lower after centrifugation respectively not
Insoluble precipitate, 60 DEG C of dryings, obtains white ZIF-8；
(b) preparation of ZIF-8/GCE
Basal electrode sanding and polishing is cleaned by ultrasonic at mirror surface, then with ultrapure water, must be handled well after natural drying at room temperature
GCE；For the ZIF-8 ultrasonic disperse that step (a) is prepared in deionized water, the dispersion liquid that preparation concentration is 1mg/mL takes 7
The μ L dispersant liquid drop is coated in the surface GCE handled well in step (c), up to ZIF-8/GCE after natural drying at room temperature；
Comparative example 3:
(a) preparation of GO@ZIF-8
The aqueous dispersions for using ultrasonic dispersion that graphene oxide GO is configured to concentration as 1mg/mL, it is above-mentioned to pipette 20mL
GO aqueous dispersions weigh 0.595g zinc nitrate and are dissolved in wherein into beaker, and adding a certain amount of agar powder keeps its final mass dense
Degree is 0.5%, until agar powder is completely dissolved, addition 30mL n,N-Dimethylformamide continues to stir 30min heating stirring,
The above-mentioned mixed solution of certain volume is pipetted while hot into the cylindrical plastic pipe of 12mm × 100mm, reaches the plastic tube
2/3rds of height do 6 plastic tubes in parallel, stand reaction 2h after being sealed later with sealed membrane at room temperature, and agar is completely solidifying
The gel of grey black is obtained after gelatinization；It weighs 3.284g 2-methylimidazole and is dissolved in the water and N that volume ratio is 1:1, N- diformazan
Base formamide in the mixed solvent after stirring and dissolving is complete, is slowly injected into 6 plastic tubes remaining three of above-mentioned gelation
/ mono- space stands 2 days after sealed membrane sealing and brings it about scattering and permeating reaction, obtains the hydrogel of grey black；From edge
6 plastic tubes are cut, the grey black jello in pipe is cut into three sections by the length of 5mm from top to bottom, then by parallel pipe
Three sections of upper, middle and lower is enriched with respectively, with the agar in n,N-Dimethylformamide dissolution jello, collects respectively after centrifugation
In lower three sections of infusible precipitate, obtain the GO@ZIF-8 composite material of three kinds of grey blacks after dry, number is 1 from top to bottom,
2,3 is spare；
(b) preparation of GO@ZIF-8/GCE
Basal electrode sanding and polishing is cleaned by ultrasonic at mirror surface, then with ultrapure water, must be handled well after natural drying at room temperature
GCE；It disperses GO@ZIF-8 No. 2 sample ultrasonics of composite material that step (a) is prepared in deionized water, is prepared into concentration
For the dispersion liquid of 1mg/mL, the 7 μ L dispersant liquid drops is taken to be coated in the surface GCE handled well, up to GO@ZIF- after natural drying at room temperature
8 complex film modified GCE.
Comparative example 4:
Basal electrode sanding and polishing is cleaned by ultrasonic at mirror surface, then with ultrapure water, must be handled well after natural drying at room temperature
GCE；It disperses RGO@ZIF-8 No. 1 sample ultrasonic of composite material that step (a) in embodiment 1 is prepared in deionized water,
It is prepared into the dispersion liquid that concentration is 1mg/mL, the 7 μ L dispersant liquid drops is taken to be coated in the surface GCE handled well, after natural drying at room temperature
Up to RGO@ZIF-8-1/GCE.
Comparative example 5:
Basal electrode sanding and polishing is cleaned by ultrasonic at mirror surface, then with ultrapure water, must be handled well after natural drying at room temperature
GCE；It disperses RGO@ZIF-8 No. 3 sample ultrasonics of composite material that step (a) in embodiment 1 is prepared in deionized water,
It is prepared into the dispersion liquid that concentration is 1mg/mL, the 7 μ L dispersant liquid drops is taken to be coated in the surface GCE handled well, after natural drying at room temperature
Up to RGO@ZIF-8-3/GCE.
A in Fig. 1, B, C are respectively 1,2, No. 3 samples of RGO@ZIF-8 composite material that step (a) is prepared in embodiment 1
The SEM of product schemes.It can be seen from the figure that ZIF-8 is grown in RGO skin lamination, partial size gradually becomes smaller with upper, middle and lower, but middle layer
In No. 2 samples No. 1 of ZIF-8 particle size upper layer and lower layer and No. 3 samples it is more uniform, partial size 30-80nm, the sample
Pattern bigger specific surface area and more active sites can be provided, therefore be more conducive to play its electrochemical catalysis activity.
Embodiment 6:
Using RGO@ZIF-8/GCE obtained by embodiment 1 as working electrode, platinum filament is to electrode, saturated calomel electrode
For reference electrode, as a comparison, according to corresponding GCE, ZIF-8/GCE, GO the@ZIF- of comparative example 1, comparative example 2 and comparative example 3
Then 8/GCE is containing 5.0mmol/L [Fe (CN) respectively as working electrode6]-3/-4With the electricity in 0.1mol/L KCl solution
Chemical impedance figure, as a result as shown in Figure 2.It can be seen from the figure that spectrogram is divided into two parts, the wherein semicircle pair under high frequency condition
Effective electronics transfer control process is answered, half circular diameter represents electronics transfer resistance (Ret)；And the linear segment of low-frequency range is corresponding
Be solutes accumulation control process.Electrochemical impedance the results show that the corresponding ZIF-8/GCE of comparative example 2 (curve b) is relative to naked
(curve a), arc radius have certain increase to GCE, illustrate that ZIF-8 increases [Fe (CN)6]3-/4-It is electric between basal electrode
The resistance of son transmitting.The correspondence of comparative example 3 GO@ZIF-8/GCE (curve c) then significantly reduces the electrochemical impedance of modified electrode,
Show that the presence of GO increases modified electrode effective active area, improves to [Fe (CN)6]3-/4-Capture ability improves electronics
Transmission efficiency.(curve d) gives the smallest arc radius to the corresponding RGO@ZIF-8/GCE of embodiment 1, illustrates RGO@ZIF-8
Composite membrane not only increases electrochemical surface area, but also increase by combining the advantage of RGO and ZIF-8 in terms of electrochemical catalysis
Strong electric conductivity, has played the concerted catalysis effect of both, has improved the catalytic performance of modified electrode.
Fig. 3 is by embodiment 1, comparative example 4 and the corresponding RGO@ZIF-8/GCE (b) of comparative example 5, RGO@ZIF-8-1/GCE
(a) and RGO@ZIF-8-3/GCE (c) is the 0.1mol/L pH's 7.5 containing 0.1mmol/L alpha-Naphthol and betanaphthol mixed liquor
Cyclic voltammetry is carried out in phosphate buffer, sweeping speed is 0.1V/s.It can obviously be observed from figure, in RGO@ZIF-
8-1/GCE is upper, and (peak current that curve a) occurs is lower, shows that electronics transfer is slow；In RGO@ZIF-8-3/GCE (on curve c)
Volt-ampere response increased, show that RGO@ZIF-8 lower layer composite material can enhance modified electrode to the electrification of naphthol isomers
Learn catalysis；And (curve b) presents highest oxidation peak current and optimal electrification to RGO@ZIF-8/GCE prepared by embodiment 1
Catalytic performance is learned, being mainly due to ZIF-8, equably growth in situ is on RGO and good electric conductivity, two components are total
The synergistic effect in terms of its electro-catalysis has been played together, is more advantageous to its application in terms of electrochemical sensing assays.
Fig. 4 is 1 gained RGO ZIF-8/GCE of embodiment pH is 7.5, to sweep speed be 100mV/s, fixed betanaphthol concentration is
DPV curve when being gradually increased when 40nmol/L with alpha-Naphthol concentration.As can be seen that when the concentration of fixed betanaphthol, alpha-Naphthol
Corresponding current-responsive is gradually increased with the increase of its concentration, and the corresponding current-responsive of betanaphthol is held essentially constant,
As is shown in said inset, when the concentration of alpha-Naphthol, its peak current is linearly closed with its concentration within the scope of 8nmol/L~100nmol/L
System, linear equation may be expressed as: Ipa(1-NAP)(μ A)=- 0.013c (nM) -0.44 (R2=0.993), α-naphthalene is known by calculating
The detection limit of phenol is respectively 2.7nmol/L.
Fig. 5 is 1 gained RGO@ZIF-8/GCE of embodiment pH is 7.5, to sweep speed be 100mV/s, fixed alpha-Naphthol concentration is
DPV curve when being gradually increased when 40nmol/L with betanaphthol concentration.As can be seen that when the concentration of fixed alpha-Naphthol, betanaphthol
Corresponding current-responsive is gradually increased with the increase of its concentration, and the corresponding current-responsive of alpha-Naphthol is held essentially constant,
As is shown in said inset, when the concentration of alpha-Naphthol, its peak current is linearly closed with its concentration within the scope of 8nmol/L~100nmol/L
System, linear equation may be expressed as: Ipa(2-NAP)(μ A)=- 0.012c (nM) -0.65 (R2=0.993), β-naphthalene is known by calculating
The detection limit of phenol is respectively 2.6nmol/L.
Table 1: present invention gained RGO@ZIF-8/GCE detects the property of alpha-Naphthol and betanaphthol and other electricity analytical methods simultaneously
It can compare
As can be seen from Table 1, it using RGO@ZIF-8/GCE of the present invention, is examined while to alpha-Naphthol and betanaphthol
Range of linearity when survey is close or is better than the reported modified electrode of some documents, but detects limit and be significantly lower than them, explanation
The complex film modified electrode of RGO@ZIF-8 has sensitive electrocatalysis characteristic and good selectivity to alpha-Naphthol and betanaphthol, because
And show better stability and sensitivity.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent conversion regime, be included within the scope of the present invention.
Claims (4)
1. a kind of complex film modified electrode of graphene oxide@ZIF-8 of reduction, it is characterised in that the substrate electricity of the modified electrode
Extremely glass-carbon electrode, decorative material are the graphene oxide@ZIF-8 composite membrane of reduction；The graphene oxide@ZIF- of the reduction
8 composite materials are in the gel-type vehicle containing graphene oxide using natural diffuseness osmosis and thermal reduction method preparation institute
；The graphene oxide is denoted as GO；The graphene oxide of the reduction is denoted as RGO；The glass-carbon electrode is denoted as GCE；
The preparation method of the complex film modified electrode of the RGO@ZIF-8, which comprises the following steps:
(a) preparation of RGO@ZIF-8
The aqueous dispersions for using ultrasonic dispersion that graphene oxide GO is configured to concentration as 1mg/mL, it is above-mentioned to pipette 20~40mL
GO aqueous dispersions weigh 0.595g zinc nitrate and are dissolved in wherein into beaker, and adding a certain amount of agar powder keeps its final mass dense
Degree is 0.5%, until agar powder is completely dissolved, addition 30mL n,N-Dimethylformamide continues to stir 30min heating stirring,
The above-mentioned mixed solution of certain volume is pipetted while hot into the cylindrical plastic pipe of 12mm × 100mm, reaches the plastic tube
2/3rds of height do 6 plastic tubes in parallel, stand reaction 2h after being sealed later with sealed membrane at room temperature, and agar is completely solidifying
The gel of grey black is obtained after gelatinization；It weighs 3.284g2- methylimidazole and is dissolved in the water and N that volume ratio is 1:1, N- diformazan
Base formamide in the mixed solvent after stirring and dissolving is complete, is slowly injected into 6 plastic tubes remaining three of above-mentioned gelation
/ mono- space stands 2 days after sealed membrane sealing and brings it about scattering and permeating reaction, obtains the hydrogel of grey black；From edge
6 plastic tubes are cut, the grey black jello in pipe is cut into three sections by the length of 5mm from top to bottom, then by parallel pipe
Three sections of upper, middle and lower is enriched with respectively, with the agar in n,N-Dimethylformamide dissolution jello, collects respectively after centrifugation
In lower three sections of infusible precipitate；Again by three 150 DEG C of grey black deposit sample dry 2h, the RGO@ZIF- of three kinds of black is obtained
8 composite materials；
(b) preparation of the complex film modified GCE of RGO@ZIF-8
Basal electrode sanding and polishing is cleaned by ultrasonic at mirror surface, then with ultrapure water, the GCE that must be handled well after natural drying at room temperature；
It disperses the RGO@ZIF-8 compound material ultrasound that step (a) is prepared in deionized water, being prepared into concentration is 1mg/mL's
Dispersion liquid takes 2~20 μ L dispersant liquid drops to be coated in the surface GCE handled well, compound up to RGO@ZIF-8 after natural drying at room temperature
Film modified GCE.
2. a kind of preparation method of the complex film modified electrode of RGO@ZIF-8 as described in claim 1, which is characterized in that step
(a) particle diameter distribution of middle layer is most uniform in resulting tri- samples of RGO@ZIF-8, partial size 30-80nm；In step (b), institute
The polishing for stating basal electrode is successively to be polished on chamois leather using the alumina powder of partial size from big to small, ultrasonic cleaning when
Between be 30s.
3. the modified electrode for the RGO@ZIF-8 that the described in any item preparation methods of claim 1 and 2 are prepared.
4. using the method for the detection naphthol isomers of modified electrode described in claims 1 to 3 any one, which is characterized in that
It, will be single containing different amounts of alpha-Naphthol and betanaphthol using the phosphate buffer of 0.1mol/L pH 7.5 as supporting electrolyte
Or both mixed solution be added in electrolytic cell, using modified electrode as working electrode, detected with differential pulse voltammetry, respectively
To the equation of linear regression of the oxidation peak current of alpha-Naphthol and betanaphthol and its concentration, using in same method measurement sample to be tested
The oxidation peak current of alpha-Naphthol and betanaphthol is acquired the content of alpha-Naphthol and betanaphthol in sample to be tested by equation of linear regression.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110492088A (en) * | 2019-09-16 | 2019-11-22 | 安徽师范大学 | A kind of ZIF-8@redox graphene sulfur loaded composite material and preparation method and lithium-sulphur cell positive electrode and lithium-sulfur cell |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103901087A (en) * | 2014-04-24 | 2014-07-02 | 青岛大学 | Modified electrode for detecting pyrocatechol and hydroquinone and preparation method thereof |
| CN108982622A (en) * | 2018-04-23 | 2018-12-11 | 中山大学 | Electrochemical sensor and preparation method thereof based on the vertical graphene composite structure of metal organic frame- |
| CN109085222A (en) * | 2018-08-10 | 2018-12-25 | 青岛科技大学 | Ion liquid functionalization graphene vibrios DNA electrochemical sensor and its preparation method and application |
| CN109100404A (en) * | 2018-08-14 | 2018-12-28 | 青岛科技大学 | Acrylic/hydrotalcite-like nano piece@ZIF-67 composite material modified electrode and preparation method thereof and detection application |
| CN109880363A (en) * | 2019-01-31 | 2019-06-14 | 曲阜师范大学 | The preparation method and application of polypyrrole@ZIF-8/ graphene nanocomposite material |
-
2019
- 2019-07-29 CN CN201910687080.5A patent/CN110412096B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103901087A (en) * | 2014-04-24 | 2014-07-02 | 青岛大学 | Modified electrode for detecting pyrocatechol and hydroquinone and preparation method thereof |
| CN108982622A (en) * | 2018-04-23 | 2018-12-11 | 中山大学 | Electrochemical sensor and preparation method thereof based on the vertical graphene composite structure of metal organic frame- |
| CN109085222A (en) * | 2018-08-10 | 2018-12-25 | 青岛科技大学 | Ion liquid functionalization graphene vibrios DNA electrochemical sensor and its preparation method and application |
| CN109100404A (en) * | 2018-08-14 | 2018-12-28 | 青岛科技大学 | Acrylic/hydrotalcite-like nano piece@ZIF-67 composite material modified electrode and preparation method thereof and detection application |
| CN109880363A (en) * | 2019-01-31 | 2019-06-14 | 曲阜师范大学 | The preparation method and application of polypyrrole@ZIF-8/ graphene nanocomposite material |
Non-Patent Citations (3)
| Title |
|---|
| DAE WOO KIM 等: "Continuous ZIF-8/reduced graphene oxide nanocoating for ultrafast oil/water separation", 《CHEMICAL ENGINEERING JOURNAL》 * |
| GEGE YU 等: "Hierarchical and hybrid RGO/ZIF-8 nanocomposite as electrochemical sensor for ultrasensitive determination of dopamine", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| TIANRONG ZHAN 等: "In situ growth of ultrathin NiFe layered double hydroxide nanosheets on reduced oxide graphene as an enhanced oxygen evolution electrocatalyst", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
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