CN106018519B - The application of complex film modified electrode of ion liquid functionalization and preparation method thereof and detection chlorophenol - Google Patents
The application of complex film modified electrode of ion liquid functionalization and preparation method thereof and detection chlorophenol Download PDFInfo
- Publication number
- CN106018519B CN106018519B CN201610546627.6A CN201610546627A CN106018519B CN 106018519 B CN106018519 B CN 106018519B CN 201610546627 A CN201610546627 A CN 201610546627A CN 106018519 B CN106018519 B CN 106018519B
- Authority
- CN
- China
- Prior art keywords
- aunps
- electrode
- modified electrode
- complex film
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 28
- 238000001514 detection method Methods 0.000 title claims abstract description 20
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- 239000010931 gold Substances 0.000 claims abstract description 14
- 229910052737 gold Inorganic materials 0.000 claims abstract description 13
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002114 nanocomposite Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 5
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 3
- 244000061458 Solanum melongena Species 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000001548 drop coating Methods 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 26
- 239000010408 film Substances 0.000 description 13
- 230000005540 biological transmission Effects 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 229910021397 glassy carbon Inorganic materials 0.000 description 7
- 239000007853 buffer solution Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- -1 Chlorophenols compound Chemical class 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- WJAAARKBHTZZSF-UHFFFAOYSA-N 3-(1h-imidazol-2-yl)butan-1-amine Chemical class NCCC(C)C1=NC=CN1 WJAAARKBHTZZSF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- HITBOAGYESUOFH-UHFFFAOYSA-N boric acid hydrochloride Chemical compound Cl.OB(O)O HITBOAGYESUOFH-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- ZPEIMTDSQAKGNT-UHFFFAOYSA-N chlorpromazine Chemical compound C1=C(Cl)C=C2N(CCCN(C)C)C3=CC=CC=C3SC2=C1 ZPEIMTDSQAKGNT-UHFFFAOYSA-N 0.000 description 1
- 229960001076 chlorpromazine Drugs 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- 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)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses the applications of complex film modified electrode of a kind of ion liquid functionalization and preparation method thereof and detection chlorophenol.Utilize the special dissolubility of ionic liquid and high electric conductivity, ion liquid functionalization graphene-gold nano grain compound made from epoxy addition is carried out to graphene oxide-gold nano grain compound as amino functional ionic liquid, corresponding complex film modified electrode is prepared for using drop-coating.Gained modified electrode surface of the invention has the characteristics that effective area is big, active site is more, good dispersion, the synergistic effect that ionic liquid, graphene and gold nano grain have been played in terms of improving Direct Electrochemistry and electrocatalysis characteristic, improves the electric conductivity and catalytic performance of modified electrode.Chlorophenol sensor of the gained based on the complex film modified electrode has many advantages, such as that detection limit is low, detection range is wide, response quickly.
Description
Technical field:
The present invention relates to complex film modified electrodes of a kind of ion liquid functionalization and its preparation method and application；Refer specifically to base
In the preparation of ion liquid functionalization graphene-gold nanoparticle composite film modified glassy carbon electrode and Electrochemical Detection application, belong to
In environment protection field.
Background technique:
Chlorophenols compound content in water body is very low, but in chlorine atom on P electronics and phenyl ring pi-electron can be formed it is stable
π-conjugated systems, most of chlorophenol all has very big toxicity, and can be accumulated in biosphere by food chain, is difficult biodegrade,
It is persistence organic pollutant in environment with " three cause " (carcinogenic, teratogenesis, mutagenesis) effect and genetoxic
The Typical Representative of (Persistent Organic Pollutants, POPs).Chlorophenols compound content in water environment is very
Low, there are great difficulties for analysis detection.Currently used detection method mainly has spectrophotometry, fluorescence method, a HPLC, GC-MS,
LC-MS, LC-MS/MS and enzyme-linked immunosorbent assay, although these methods have reliable sensitivity and lower detection limit,
Expensive equipment, the application that sample pretreatment is complicated, operation time-consuming is many and diverse, is unable to the disadvantages of on-site test limits them significantly
[Banimuslem H,Hassan A,Basova T,Gulmez A D,Tuncel S,Durmus M,Gurek A G,Ahsen
V.Copper phthalocyanine/single walled carbon nanotubes hybrid thin films for
pentachlorophenol detection.Sensor Actuat.B 2014,190,990-998.].Electrochemical sensing method because
Its analyze that speed is fast, instrument is simple, easy to operate, low in cost, high sensitivity, selectivity are good and can real-time detection etc. it is excellent
Gesture is applied in the context of detection of chlorophenols compound, is such as based on ZnSe-CTAB/GCE, HRP/Au/GCE, NNH-
The detection of the electrochemical sensor parachlorphenol of MWCNTs/GCE, CD/GRs/CPE composite modified electrode.But that reports at present is such
Electrochemical sensor exist mostly as construct it is complicated, need medium or probe, need " Ping-Pong " of biological enzyme be catalyzed and
The defects of parachlorphenol catalysis oxidation ability is poor is highly detrimental to their practical application and extensive development.Therefore, searching has
The novel electrode decorative material of high electrocatalysis characteristic, developing still has very big challenge for detecting the electrochemical sensor of chlorophenol.
Graphene (Grpahene, GR) be it is closely regularly arranged by single layer of carbon atom, carbon atom is with sp2Hydridization is mutually bonded
Six-membered carbon ring is formed, the lamella (see Fig. 2) with cellular two-dimension plane structure is then extended to form, is to send out in the world at present
Existing most thin carbon material.GR is with the special physics such as at low cost, large specific surface area, thermal stability height, good conductivity, chemistry
And mechanical performance, it has obtained answering extensively in fields such as nanoelectronic, sensor, battery, supercapacitor and energy storage in recent years
With [Gao Z, Wang J, Li Z, Yang W, Wang B, Hou M, He Y, Liu Q, Mann T, Yang P, Zhang M, Liu
L.Graphene Nanosheet/Ni2+/Al3+Layered Double-Hydroxide Composite as a Novel
Electrode for a Supercapacitor.Chem.Mater.2011,23,3509-3516.].Wherein repaired as electrode
Exterior material, due to good electric conductivity and big surface area, the use of GR nanometer sheet not only increases modified electrode to substrate point
The capture ability of son, and its electron transmission is promoted, show excellent electrocatalysis characteristic.It is based on as researcher has used
The electrochemical sensing method of GR modified electrode has detected phosphoric acid ester insecticide, chlorpromazine and 4- in environment with sensitivity
The environmental contaminants such as amino-phenol, catechol, resorcinol and hydroquinone [Meng X, Yin H, Xu M, Ai S, Zhu
J.Electrochemical determination of nonylphenol based on ionic liquid-
functionalized graphene nanosheet modified glassy carbon electrode and its
interaction with DNA.J.Solid State Electrochem.2012,16:2837–2843.].Currently, GR is logical
Often prepared by electronation graphene oxide (GO), but GR is easy to that Severe aggregation occurs in chemical reduction procedure, and
The internal performance that cannot really reflect GR nanometers of monolithics hinders its electron transmission as electrode modified material when significantly
Energy.In order to solve this problem, functional nano-composites first usually are prepared by substrate of monoatomic layer GO nanometer sheet, then carry out
In-situ reducing GO, prepares the GR nano-complex of reduction form, to make GR reach the dispersion of molecular level in composite membrane, most
Limits play the synergistic effect that each component in nano composite membrane improves electron transmission.
Gold nanoparticle (AuNPs) also has good electric conductivity other than with skin effect and quantum size effect
And biocompatibility, can reduce greatly electron donor between receptor at a distance from, improve electronics in interelectrode transmission rate, in electrification
Learning sensory field has important application.But AuNPs generally also will appear agglomeration, drastically influences it and further applies.
Therefore, compound of the preparation based on AuNPs is the important thinking for solving the problems, such as this.
Amino functional ionic liquid is not only a kind of high conductivity, the green solvent with special solubility property, and
Ring-opening reaction can occur with a large amount of epoxide ring in the surface GO for its functional amino, and the composite material table based on GO/GR is arrived in modification
Face.Due to special dissolubility, a large amount of charge and high electric conductivity, the introducing of ionic liquid can greatly improve GO/GR
Dispersibility, stability and the electric conductivity of sill.Currently, using amino functional ionic liquid to GO-AuNPs composite material into
Row epoxy ring opening reaction prepares ion liquid functionalization graphene-gold nano grain compound (IL-GR-AuNPs), and is based on
The research of the complexes membrane modified electrode and its parachlorphenol context of detection has not been reported.The present invention will use electrostatic assembly and be total to
Valence modifies method and prepares IL-GR-AuNPs, prepares corresponding modified electrode and is used for the detection of parachlorphenol.
IL-GR-AuNPs is prepared using electrostatic assembly and covalent modification method, GR nanometer sheet can not only be made successfully to wrap AuNPs
The problem of covering, GR nanometer sheet and AuNPs is effectively inhibited to assemble, improves the specific surface area and electric conductivity of composite material, Er Qietong
Cross the covalent modification of IL, the electric conductivity, dispersibility and stability of compound can also be further increased, give full play to IL, GR and
Advantage of the AuNPs in terms of electrode modification compensates for defect when they are used alone.IL-GR-AuNPs compound is used for
Modified glassy carbon electrode, the nano composite membrane can provide more active sites, higher electric conductivity and good dispersibility, fill
The synergistic effect of three kinds of components is waved in distribution, to improve Direct Electrochemistry and electrocatalysis of the tested substance on modified electrode
Can, it is of great significance to novel high-sensitivity electrochemical detection method is established.
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 kind complex film modified electrode of ion liquid functionalization；I.e. by amino functional ionic liquid to graphene oxide-gold nano grain
Compound carries out IL-GR-AuNPs compound made from epoxy addition, and prepares corresponding modified electrode with the compound.
A kind of complex film modified electrode of ion liquid functionalization provided by the present invention, it is characterised in that the ionic liquid
The complex film modified electrode of functionalization is by glass-carbon electrode as basal electrode, and ion liquid functionalization composite membrane is as electrode modification material
Material composition；The ion liquid functionalization composite membrane is by amino functional ionic liquid to graphene oxide-gold nano grain
Compound carries out ion liquid functionalization graphene-gold nano grain compound made from epoxy addition；The glass-carbon electrode note
For GCE；The graphene oxide is denoted as GO, and the graphene is denoted as GR, and the gold nano grain is denoted as AuNPs；The ion
Liquid is 1- methyl -3- aminopropyl imidazoles hydrobromate, is denoted as IL, structural formula is as follows:
The graphene oxide is denoted as GO, and the graphene is denoted as GR, and the ionic liquid is 1- butyl -3- aminopropyl miaow
Four Chlorine borate of azoles, is denoted as IL, and structural formula is as follows:
It is special the second object of the present invention is to provide a kind of preparation method of complex film modified electrode of ion liquid functionalization
Sign be comprising the following specific steps
(a) preparation of AuNPs dispersion liquid
Taking 100mL mass concentration is 0.01% HAuCl4Aqueous solution is heated to boiling, is stirred continuously down and is slowly added to
The sodium citrate solution that 1.5mL mass fraction is 1% continues agitating and heating and boils 15min, and solution becomes aubergine and is cooled to room
Temperature is restored with deionized water to original volume, and AuNPs dispersion liquid is obtained；
(b) preparation of GO-AuNPs nanocomposite
GO is prepared using hummer method, and a certain amount of resulting GO is dispersed in water, makes its concentration 5mg/mL, ultrasound
Dispersion 2 hours, 3000rpm are centrifuged 10min and remove undispersed GO, the GO dispersion liquid removed；The 20mL GO dispersion liquid is taken,
It is stirred continuously down the AuNPs dispersion liquid that 10mL is slowly added dropwise thereto, rear room temperature is sufficiently mixed and stirs under confined conditions 12 hours,
After 5000rmp is centrifuged 10min, gained brownish black precipitating is GO-AuNPs compound；
(c) preparation of IL-GR-AuNPs composite material
It weighs 10~40mg of GO-AuNPs compound obtained in step (b) to be scattered in 20mL deionized water, thereto
30min is ultrasonically treated after being slowly added to 5~10mg IL and 5~10mg KOH；Dispersion liquid after ultrasound is heated at 80 DEG C and is stirred
Mix reflux for 24 hours, obtained product 8000rmp centrifugation 5min is successively washed 3 times with water and dehydrated alcohol, gained black solid object
Matter is IL-GR-AuNPs compound；
(d) preparation of the complex film modified glass-carbon electrode of IL-GR-AuNPs
IL-GR-AuNPs composite material obtained in step (c) is configured to the slurry that concentration is 1mg/mL with deionized water
Shape liquid, takes 6~12 μ L pulpous state drop-coated on the surface of glass-carbon electrode, and naturally dry obtains IL-GR-AuNPs/GCE modification electricity
Pole.
It is characterized in that IL-GR-AuNPs compound described in step (c) is IL multiple with GO-AuNPs under alkaline condition
It closes the epoxide ring in object on GO molecule and occurs what open loop generated；The IL-GR-AuNPs compound is IL covalent modification by GR
The AuNPs composite surface of cladding can be stabilized 2 days, and the then sedimentation completely within 10min of GO-AuNPs hybrid,
The dispersibility and stability of the IL-GR-AuNPs compound are significantly improved.
The three of the object of the invention are to provide a kind of complex film modified electrode of ion liquid functionalization and are preparing electrochemical sensing
Application in terms of device.Specifically, the exactly described complex film modified electrode of ion liquid functionalization the answering in chlorophenol context of detection
With.
More specifically, the chlorophenol is 2,4- Dichlorophenol.
The present invention utilizes the advantages that special solubility property of IL and high electric conductivity, by covalent modification method by amino function
The IL of energyization introduces GR-AuNPs hybrid surface, prepares IL-GR-AuNPs compound；IL-GR- is prepared for using drop-coating
AuNPs/GCE, and constructed the third generation chlorophenol electrochemical sensor based on IL-GR-AuNPs composite membrane.
Compared with prior art, major advantage is: the complex film modified electrode of present invention gained is in terms of electro-catalysis chlorophenol
Played IL, GR and AuNPs synergistic effect: AuNPs improves the specific surface area and electric conductivity of composite membrane, with into inhibiting GR to receive
The aggregation of rice piece；Compound is prepared by substrate of GR nanometer sheet, effectively inhibits the aggregation of AuNPs, the two electrostatic assembly improves
The electro-catalysis and electron transmission efficiency of compound；The covalent modification of IL further enhances the conduction of GR-AuNPs hybrid
Property, dispersibility and stability；IL-GR-AuNPs composite membrane is substantially increased as the bridge between chlorophenol and basal electrode to chlorine
The capture and electro-catalysis ability of phenol.Specifically, the electrochemical catalysis of IL-GR-AuNPs composite membrane parachlorphenol produces unexpected
Technical effect；The electrocatalytic effect of the complex film modified electrode parachlorphenol of gained of the invention, with individual AuNPs or
GR, or compared with the GR-AuNPs compound obtained by chemical reduction method, all tool is significantly improved；Biography of the present invention
Sensor has the characteristics that quick response, Monitoring lower-cut are low, detection range is wide and is suitable for on-site test, method is easy to operate,
Mild condition, preparation cost are low.
Detailed description of the invention:
Fig. 1 for 2 gained IL-GO-AuNPs compound of embodiment 2 institute of electron scanning micrograph (b) and comparative example
Obtain the electron scanning micrograph (a) of GO-AuNPs compound.
Fig. 2 is the optical photograph of 2 gained IL-GO-AuNPs (a) of embodiment and 2 gained GO-AuNPs (b) of comparative example, left figure
The photo of dispersibility when for 0min in water, right figure be 120min after dispersibility photo.
Fig. 3 is embodiment 2 (c), modified electrode obtained by comparative example 1 (a), comparative example 2 (b) is containing 5.0mmol/L [Fe
(CN)6]3-/4-With the cyclic voltammogram in 0.1mol/L KCl solution.
Fig. 4 is that the IL-GO-AuNPs in embodiment 2 is repaired with the bare electrode in comparative example 1, the GO-AuNPs in comparative example 2
It adorns electrode and is containing 5.0mmol/L [Fe (CN)6]-3/-4With the impedance diagram in 0.1mol/L KCl solution.
Fig. 5 is embodiment 2 (c), modified electrode obtained by comparative example 1 (a), comparative example 2 (b) is containing 0.2 μm of ol/mL2,4-
In the PBS buffer solution of the pH=8 of Dichlorophenol, sweep speed be 100mV/s when cyclic voltammogram.
Fig. 6 be IL-GO-AuNPs modified electrode obtained in embodiment 2 in the PBS buffer solution of pH=8, sweep speed and be
When 100mV/s, with the DPV curve that 2,4- Dichlorophenol concentration constantly increases, illustration is oxidation peak current and 2,4- Dichlorophenol concentration
Linear relationship.
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 AuNPs dispersion liquid
Taking 100mL mass concentration is 0.01% HAuCl4Aqueous solution is heated to boiling, is stirred continuously down and is slowly added to
The sodium citrate solution that 1.5mL mass fraction is 1% continues agitating and heating and boils 15min, and solution becomes aubergine and is cooled to room
Temperature is restored with deionized water to original volume, and AuNPs dispersion liquid is obtained；
(b) preparation of GO-AuNPs nanocomposite
GO is prepared using hummer method, and a certain amount of resulting GO is dispersed in water, makes its concentration 5mg/mL, ultrasound
Dispersion 2 hours, 3000rpm are centrifuged 10min and remove undispersed GO, the GO dispersion liquid removed；The 20mL GO dispersion liquid is taken,
It is stirred continuously down the AuNPs dispersion liquid that 10mL is slowly added dropwise thereto, rear room temperature is sufficiently mixed and stirs under confined conditions 12 hours,
After 5000rmp is centrifuged 10min, gained brownish black precipitating is GO-AuNPs compound；
(c) preparation of IL-GR-AuNPs composite material
It weighs GO-AuNPs compound 10mg obtained in step (b) to be scattered in 20mL deionized water, thereto slowly
30min is ultrasonically treated after 5mg IL and 5mg KOH is added；By the dispersion liquid after ultrasound, heating stirring reflux for 24 hours, is obtained at 80 DEG C
The product 8000rmp centrifugation 5min arrived, is successively washed 3 times with water and dehydrated alcohol, gained black solid material is IL-GR-
AuNPs compound；
(d) preparation of the complex film modified glass-carbon electrode of IL-GR-AuNPs
IL-GR-AuNPs composite material obtained in step (c) is configured to the slurry that concentration is 1mg/mL with deionized water
Shape liquid takes the 8 μ L pulpous state drop-coated on the surface of glass-carbon electrode, and naturally dry obtains IL-GR-AuNPs/GCE modified electrode.
Embodiment 2:
(a) preparation of AuNPs
According to the method and condition preparation in step (a) in embodiment 1；
(b) preparation of GO-AuNPs nanocomposite
According to the method and condition preparation in step (b) in embodiment 1；
(c) preparation of IL-GR-AuNPs composite material
It weighs GO-AuNPs compound 20mg obtained in step (b) to be scattered in 20mL deionized water, thereto slowly
30min is ultrasonically treated after 10mg IL and 10mg KOH is added；By the dispersion liquid after ultrasound, heating stirring flows back for 24 hours at 80 DEG C,
Obtained product 8000rmp centrifugation 5min, is successively washed 3 times with water and dehydrated alcohol, gained black solid material is IL-
GR-AuNPs compound；
(d) preparation of IL-GR-AuNPs composite material modified glassy carbon electrode
According to the method and condition preparation in step (d) in embodiment 1.
Embodiment 3:
(a) preparation of AuNPs
According to the method and condition preparation in step (a) in embodiment 1；
(b) preparation of GO-AuNPs nanocomposite
According to the method and condition preparation in step (b) in embodiment 1；
(c) preparation of IL-GR-AuNPs composite material
It weighs GO-AuNPs compound 30mg obtained in step (b) to be scattered in 20mL deionized water, thereto slowly
30min is ultrasonically treated after 10mg IL and 10mg KOH is added；By the dispersion liquid after ultrasound, heating stirring flows back for 24 hours at 80 DEG C,
Obtained product 8000rmp centrifugation 5min, is successively washed 3 times with water and dehydrated alcohol, gained black solid material is IL-
GR-AuNPs compound；
(d) preparation of IL-GR-AuNPs composite material modified glassy carbon electrode
IL-GR-AuNPs composite material obtained in step (c) is configured to the slurry that concentration is 1mg/mL with deionized water
Shape liquid takes the 10 μ L pulpous state drop-coated on the surface of glass-carbon electrode, and naturally dry obtains IL-GR-AuNPs/ GCE modified electrode.
Embodiment 4:
(a) preparation of AuNPs
According to the method and condition preparation in step (a) in embodiment 1；
(b) preparation of GO-AuNPs nanocomposite
According to the method and condition preparation in step (b) in embodiment 1；
(c) preparation of IL-GR-AuNPs composite material
It weighs GO-AuNPs compound 40mg obtained in step (b) to be scattered in 20mL deionized water, thereto slowly
30min is ultrasonically treated after 10mg IL and 10mg KOH is added；By the dispersion liquid after ultrasound, heating stirring flows back for 24 hours at 80 DEG C,
Obtained product 8000rmp centrifugation 5min, is successively washed 3 times with water and dehydrated alcohol, gained black solid material is IL-
GR-AuNPs compound；
(d) preparation of IL-GR-AuNPs composite material modified glassy carbon electrode
According to the method and condition preparation in step (d) in embodiment 3.
Comparative example 1:
Directly use naked GCE.
Comparative example 2:
According to the above-mentioned method for preparing modified electrode, the dispersion that concentration is 1mg/mL is prepared into GO-AuNPs composite material
Liquid takes 8 μ L drop coatings in the glassy carbon electrode surface of milled, obtains GO-AuNPs/GCE after natural drying.
Fig. 1 for 2 gained IL-GR-AuNPs compound of embodiment 2 institute of electron scanning micrograph (b) and comparative example
Obtain the electron scanning micrograph (a) of GO-AuNPs compound.As can be seen that being used as substrate GO from scanning electron microscope (a) figure
Nanometer sheet has a clearly wrinkle striped, the spherical AuNPs of random distribution on its lamella, partial size about 100~
150nm.After IL covalent modification, the boundary of AuNPs obviously becomes weak in IL-GR-AuNPs (figure b) compound, and GR nanometer sheet
Pleated structure almost disappear, the surface of complexes membrane becomes more smooth compared to the GO-AuNPs of non-IL functionalization, this master
If because IL is by occurring ring-opening reaction covalent modification caused by its surface with the epoxide ring on the surface GO.
Fig. 2 is the optical photograph of 2 gained IL-GR-AuNPs (a) of embodiment and 2 gained GO-AuNPs (b) of comparative example.Left figure
The photo of dispersibility when for for 0min in water, right figure be 120min after dispersibility photo.It can be seen from the figure that IL
Product IL-GR-AuNPs after functionalization has good dispersibility in water, also has no sedimentation after 120min；And non-function
The bad dispersibility of the product GO-AuNPs of change in water, this is primarily due to the covalent introducing of IL, can make composite surface band
Charge, simultaneously because the presence of IL special dissolubility and its amino functional group, had IL-GR-AuNPs compound both
Preferable hydrophily, and there is charging property, to have good dispersibility, created condition to prepare modified electrode.
Fig. 3 is embodiment 2 (c), modified electrode obtained by comparative example 1 (a), comparative example 2 (b) is containing 5.0mmol/L [Fe
(CN)6]3-/4-With the cyclic voltammogram in 0.1mol/L KCl solution.A curve is the bare electrode in comparative example 1 in [Fe in figure
(CN)6]3-/4-With the cyclic voltammetry curve in 0.1mol/L KCl solution, GO-AuNPs modification electricity in b curve comparison example 2 in figure
The cyclic voltammetry curve of pole, compared to the GCE in comparative example 1, the redox current of the GO-AuNPs/GCE in comparative example 2 increases
It is big, this is because improving electrode interface to [Fe (CN) after AuNPs and the GO electrostatic assembly with high conductivity6]3-/4-'s
Capture ability, and improve its electron transmission efficiency between basal electrode.And c curve is the IL- in embodiment 2 in figure
The cyclic voltammetry curve of GR-AuNPs modified electrode, compared with GCE, GO-AuNPs/GCE in comparative example 1,2, IL-GO-
The redox current of AuNPs/GCE is maximum, this explanation is after covalent modification introduces IL, and IL-GO-AuNPs composite membrane is into one
Step improves the electrocatalysis characteristic of composite membrane.
Fig. 4 is that the IL-GR-AuNPs in embodiment 2 is repaired with the bare electrode in comparative example 1, the GO-AuNPs in comparative example 2
It adorns electrode and is containing 5.0mmol/L [Fe (CN)6]3-/4-With the impedance diagram in 0.1mol/L KCl solution.It can be seen from the figure that
Spectrogram is divided into two parts, and wherein the semicircle under high frequency condition corresponds to effective electronics transfer control process, and half circular diameter represents electricity
Sub- transfer resistance (Ret)；And it is solutes accumulation control process that the linear segment of low-frequency range is corresponding.Electrochemical impedance result is aobvious
Show, the GO-AuNPs/GCE in comparative example 2 is significantly reduced relative to naked GCE, arc radius, illustrates the AuNPs of high conductivity
With the resistance for reducing electron transmission after GO electrostatic assembly.The corresponding IL-GO-AuNPs/GCE of embodiment 2, arc radius is most
It is small, it is almost in straight line, this illustrates that the covalent introducing of IL further enhances the electric conductivity of IL-GO-AuNPs/GCE, thus
Faster electron transport rate is shown, while also illustrating that composite material successfully modifies the surface for having arrived electrode.
Fig. 5 is embodiment 2 (c), modified electrode obtained by comparative example 1 (a), comparative example 2 (b) is containing 0.2 μm of ol/mL2,4-
In the PBS buffer solution of the pH=8 of Dichlorophenol, sweep speed be 100mV/s when cyclic voltammogram.According to figure as can be seen that electrode exists
Contain and there was only oxidation peak in the PBS buffer solution of 2,4- Dichlorophenol, illustrates that the reaction is that irreversible oxidation reaction and electronics pass
Pass process.It can be seen from the figure that (oxidation peak current of the corresponding bare electrode of curve a) is minimum for comparative example 1；In comparative example 2 (b)
The oxidation peak current of corresponding GO-AuNPs/GCE electrode is significantly increased than the peak current of the bare electrode in comparative example 1；Embodiment 2
The redox peak current of IL-GR-AuNPs/GCE electrode after the middle functionalization with IL is maximum, illustrates with GO-AuNPs composite wood
Expect that the electron transport rate of the electrode of modification improves, and the electron transport rate of IL-GR-AuNPs/GCE further increases, and leads
It electrically further enhances, shows best electrocatalysis characteristic.
Fig. 6 be IL-GR-AuNPs modified electrode obtained in embodiment 2 in the PBS buffer solution of pH=8, sweep speed and be
When 100mV/s, with the DPV curve that 2,4- Dichlorophenol concentration constantly increases, illustration is oxidation peak current and 2,4- Dichlorophenol concentration
Linear relationship.With the increase of 2,4- Dichlorophenol concentration, oxidation peak current is gradually increased.When 2,4- Dichlorophenol concentration is 0.01
When~165 μm of ol/L, peak current and 2,4- Dichlorophenol concentration is in a linear relationship, as shown in illustration in Fig. 6, linear equation Ip
(μ A)=- 1.523C (μm ol/L) -0.1169 (R=0.9996), detection are limited to 3.3nM.Its performance is much better than GR-AuNPs/
GCE (detection range is 0.5~48 μm of ol/L, and detection is limited to 50.6nM).It can be seen that IL-GR- obtained in embodiment 2
The features such as 2, the 4- Dichlorophenol electrochemical sensor of AuNPs modified electrode building has the range of linearity wide, and detection limit is low.
Claims (5)
1. a kind of complex film modified electrode of ion liquid functionalization, it is characterised in that the ion liquid functionalization is complex film modified
By glass-carbon electrode as basal electrode, ion liquid functionalization composite membrane forms electrode as electrode modified material；The ion
Liquid functional composite membrane is to carry out epoxy to graphene oxide-gold nano grain compound by amino functional ionic liquid to open
The graphene of ion liquid functionalization made from ring-gold nano grain compound；The glass-carbon electrode is denoted as GCE；The oxidation stone
Black alkene is denoted as GO, and the graphene is denoted as GR, and the gold nano grain is denoted as AuNPs；The ionic liquid is 1- methyl -3- ammonia
Propyl imidazole hydrobromate is denoted as IL, and structural formula is as follows:
The preparation method of the complex film modified electrode of ion liquid functionalization, it is characterised in that comprising the following specific steps
(a) preparation of AuNPs dispersion liquid
Taking 100mL mass concentration is 0.01% HAuCl4Aqueous solution is heated to boiling, and is stirred continuously down and is slowly added to 1.5mL mass
Score be 1% sodium citrate solution, continue agitating and heating boil 15min, solution becomes aubergine and is cooled to room temperature, spend from
Sub- water restores to original volume, obtains AuNPs dispersion liquid；
(b) preparation of GO-AuNPs nanocomposite
GO is prepared using hummer method, and a certain amount of resulting GO is dispersed in water, makes its concentration 5mg/mL, ultrasonic disperse
2 hours, 3000rpm was centrifuged 10min and removes undispersed GO, the GO dispersion liquid removed；The 20mL GO dispersion liquid is taken, constantly
The AuNPs dispersion liquid of 10mL is slowly added dropwise under stirring thereto, is sufficiently mixed rear room temperature and stirs under confined conditions 12 hours,
After 5000rmp is centrifuged 10min, gained brownish black precipitating is GO-AuNPs compound；
(c) preparation of IL-GR-AuNPs composite material
It weighs 10~40mg of GO-AuNPs compound obtained in step (b) to be scattered in 20mL deionized water, thereto slowly
30min is ultrasonically treated after 5~10mg IL and 5~10mg KOH is added；By the dispersion liquid after ultrasound, heating stirring is returned at 80 DEG C
For 24 hours, obtained product 8000rmp centrifugation 5min is successively washed 3 times with water and dehydrated alcohol, gained black solid material is stream
For IL-GR-AuNPs compound；
(d) preparation of the complex film modified glass-carbon electrode of IL-GR-AuNPs
IL-GR-AuNPs composite material obtained in step (c) is configured to the pulpous state liquid that concentration is 1mg/mL with deionized water,
Take 6~12 μ L pulpous state drop-coated on the surface of glass-carbon electrode, naturally dry obtains IL-GR-AuNPs/GCE modified electrode.
2. a kind of preparation method of the complex film modified electrode of ion liquid functionalization according to claim 1, feature exist
The IL-GR-AuNPs compound described in step (c) is IL under alkaline condition and on GO molecule in GO-AuNPs compound
Epoxide ring occurs what open loop generated；The IL-GR-AuNPs compound is IL covalent modification in the AuNPs compound coated by GR
Surface can be stabilized 2 days, and the then sedimentation completely within 10min of GO-AuNPs hybrid, the IL-GR-AuNPs are multiple
The dispersibility and stability for closing object are significantly improved.
3. the complex film modified electrode of a kind of ion liquid functionalization as claimed in claim 1 or 2 is in terms of preparing electrochemical sensor
Application.
4. a kind of application of the complex film modified electrode of ion liquid functionalization according to claim 3, it is characterised in that should
Modified electrode can be used for the detection of chlorophenol.
5. a kind of application of the complex film modified electrode of ion liquid functionalization according to claim 4, it is characterised in that institute
Stating chlorophenol is 2,4- Dichlorophenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610546627.6A CN106018519B (en) | 2016-07-12 | 2016-07-12 | The application of complex film modified electrode of ion liquid functionalization and preparation method thereof and detection chlorophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610546627.6A CN106018519B (en) | 2016-07-12 | 2016-07-12 | The application of complex film modified electrode of ion liquid functionalization and preparation method thereof and detection chlorophenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106018519A CN106018519A (en) | 2016-10-12 |
| CN106018519B true CN106018519B (en) | 2019-04-05 |
Family
ID=57110044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610546627.6A Expired - Fee Related CN106018519B (en) | 2016-07-12 | 2016-07-12 | The application of complex film modified electrode of ion liquid functionalization and preparation method thereof and detection chlorophenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106018519B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107192752B (en) * | 2017-08-01 | 2019-07-05 | 信阳师范学院 | A kind of chemically modified electrode and preparation method thereof for highly sensitive detection nonyl phenol |
| CN109085222B (en) * | 2018-08-10 | 2020-07-28 | 青岛科技大学 | Ionic liquid functionalized graphene vibrio DNA electrochemical sensor and preparation method and application thereof |
| CN109142476B (en) * | 2018-08-14 | 2020-07-07 | 青岛科技大学 | Functionalized molybdenum disulfide nanosheet composite membrane modified electrode and preparation method and detection application thereof |
| CN110455895B (en) * | 2019-08-20 | 2021-09-10 | 青岛科技大学 | Electrochemical DNA sensor of thionine functionalized composite membrane and application thereof |
| CN111514930B (en) * | 2020-04-30 | 2023-07-25 | 山东理工大学 | Ionic liquid stable monoatomic catalyst and preparation method and application thereof |
| CN112415070B (en) * | 2020-10-27 | 2022-12-06 | 浙江理工大学 | Preparation method of immunosensor modified electrode for silk fibroin detection |
| CN116441555B (en) * | 2023-06-16 | 2023-08-22 | 北京建工环境修复股份有限公司 | Functionalized gold nanorod probe, preparation method and application thereof in pentachlorophenol dark field microscopic imaging detection |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102914570A (en) * | 2012-06-14 | 2013-02-06 | 青岛科技大学 | Method for detecting glutathione based on nanogold and thionine signal amplification |
| CN103394326A (en) * | 2013-08-20 | 2013-11-20 | 青岛科技大学 | Amino functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
| CN105223244A (en) * | 2015-09-24 | 2016-01-06 | 济南大学 | A kind of preparation method and application detecting the trace electrochemical sensor of vanillic aldehyde |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101212012B1 (en) * | 2010-08-17 | 2012-12-13 | 중앙대학교 산학협력단 | Patterning method of graphene using microfluidic systems |
| US9484158B2 (en) * | 2012-02-17 | 2016-11-01 | The Trustees Of Princeton University | Graphene-ionic liquid composites |
| TWI522613B (en) * | 2014-01-10 | 2016-02-21 | 國立中央大學 | Sensing electrode of an enzyme-based sensor and method for manufacturing the same |
| CA2957918A1 (en) * | 2014-08-11 | 2016-02-18 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Aligned graphene-carbon nanotube porous carbon composite |
-
2016
- 2016-07-12 CN CN201610546627.6A patent/CN106018519B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102914570A (en) * | 2012-06-14 | 2013-02-06 | 青岛科技大学 | Method for detecting glutathione based on nanogold and thionine signal amplification |
| CN103394326A (en) * | 2013-08-20 | 2013-11-20 | 青岛科技大学 | Amino functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
| CN105223244A (en) * | 2015-09-24 | 2016-01-06 | 济南大学 | A kind of preparation method and application detecting the trace electrochemical sensor of vanillic aldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106018519A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106018519B (en) | The application of complex film modified electrode of ion liquid functionalization and preparation method thereof and detection chlorophenol | |
| Agnihotri et al. | Transition metal oxides in electrochemical and bio sensing: A state-of-art review | |
| Liu et al. | Recent advances in nanomaterial-enabled screen-printed electrochemical sensors for heavy metal detection | |
| Lu et al. | A screen-printed carbon electrode modified with a bismuth film and gold nanoparticles for simultaneous stripping voltammetric determination of Zn (II), Pb (II) and Cu (II) | |
| Wang et al. | Surface morphology-controllable magnetic covalent organic frameworks: A novel electrocatalyst for simultaneously high-performance detection of p-nitrophenol and o-nitrophenol | |
| Wen et al. | N-doped reduced graphene oxide/MnO2 nanocomposite for electrochemical detection of Hg2+ by square wave stripping voltammetry | |
| Pan et al. | Nanocomposite based on graphene and intercalated covalent organic frameworks with hydrosulphonyl groups for electrochemical determination of heavy metal ions | |
| Yang et al. | An electrochemical immunosensor for rapid determination of clenbuterol by using magnetic nanocomposites to modify screen printed carbon electrode based on competitive immunoassay mode | |
| Jiang et al. | A non-enzymatic hydrogen peroxide sensor based on a glassy carbon electrode modified with cuprous oxide and nitrogen-doped graphene in a nafion matrix | |
| CN103344689B (en) | Based on Fe 3o 4magnetic pole, the preparations and applicatio of-AuNPs magnetic composite nanoparticles immobilization acetylcholinesteraseelectrochemistry | |
| Sun et al. | Simultaneous electrochemical determination of guanosine and adenosine with graphene–ZrO2 nanocomposite modified carbon ionic liquid electrode | |
| Hu et al. | Electrochemical detection of rutin with a carbon ionic liquid electrode modified by Nafion, graphene oxide and ionic liquid composite | |
| Chen et al. | Simultaneous determination of dihydroxybenzene isomers using glass carbon electrode modified with 3D CNT-graphene decorated with au nanoparticles | |
| Huang et al. | Fabrication of rGO/MXene-Pd/rGO hierarchical framework as high-performance electrochemical sensing platform for luteolin detection | |
| CN105628764A (en) | Uric acid detection electrochemical sensor and preparation and application thereof | |
| Dai et al. | Nickel‐Foam‐Supported Co3O4 Nanosheets/PPy Nanowire Heterostructure for Non‐enzymatic Glucose Sensing | |
| Xu et al. | Highly porous magnetite/graphene nanocomposites for a solid-state electrochemiluminescence sensor on paper-based chips | |
| Yi et al. | Three-dimensional flower-like nickel oxide/graphene nanostructures for electrochemical detection of environmental nitrite | |
| Yuan et al. | Layered titanate nanosheets as an enhanced sensing platform for ultrasensitive stripping voltammetric detection of mercury (II) | |
| Guo et al. | Amperometric sensing of hydrazine using a magnetic glassy carbon electrode modified with a ternary composite prepared from Prussian blue, Fe 3 O 4 nanoparticles, and reduced graphene oxide | |
| Zhang et al. | A highly sensitive electrochemical sensor for bisphenol A using cetyltrimethylammonium bromide functionalized carbon nanohorn modified electrode | |
| CN106442666B (en) | Ion liquid functionalization azotized carbon nano sheet modified electrode and its preparation and the application for detecting chlorophenol | |
| CN107941889A (en) | A kind of preparation and electrochemical sensing application study of stannic oxide three-dimensional grapheme nanocomposite fixing protein modified electrode | |
| Ma et al. | Voltammetric determination of hydrogen peroxide using AuCu nanoparticles attached on polypyrrole-modified 2D metal-organic framework nanosheets | |
| Nouri et al. | A gr/αFe2O3/carbon paste electrode developed as an electrochemical sensor for determination of rizatriptan benzoate: an antimigraine drug |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201211 Address after: 1607, building 49, No.3, Queshan Yunfeng Road, Gaofeng community, Dalang street, Longhua District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Hongyue Information Technology Co.,Ltd. Address before: 266000 Qingdao University of Science & Technology, 53 Zhengzhou Road, Shibei District, Qingdao, Shandong Patentee before: Qingdao University Of Science And Technology Effective date of registration: 20201211 Address after: 241000 No.32 Chunjiang Road, Qingshui street, Jiujiang District, Wuhu City, Anhui Province Patentee after: Zhuo Suxu Address before: 1607, building 49, No.3, Queshan Yunfeng Road, Gaofeng community, Dalang street, Longhua District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Hongyue Information Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221009 Address after: 271000 Annex Building 103, Building 9, Taishan Wisdom Valley, Yitianmen Street, High tech Zone, Tai'an City, Shandong Province Patentee after: Naklear (Shandong) New Material Technology Co.,Ltd. Address before: 241000 No.32 Chunjiang Road, Qingshui street, Jiujiang District, Wuhu City, Anhui Province Patentee before: Zhuo Suxu |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190405 |