CN106018519A - Ionic liquid functional composite membrane modified electrode and preparation method and application thereof to detection of chlorophenol - Google Patents
Ionic liquid functional composite membrane modified electrode and preparation method and application thereof to detection of chlorophenol Download PDFInfo
- Publication number
- CN106018519A CN106018519A CN201610546627.6A CN201610546627A CN106018519A CN 106018519 A CN106018519 A CN 106018519A CN 201610546627 A CN201610546627 A CN 201610546627A CN 106018519 A CN106018519 A CN 106018519A
- Authority
- CN
- China
- Prior art keywords
- aunps
- complex
- modified electrode
- electrode
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000001514 detection method Methods 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 title claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 16
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- 239000010931 gold Substances 0.000 claims abstract description 12
- 229910052737 gold Inorganic materials 0.000 claims abstract description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- 230000005518 electrochemistry Effects 0.000 claims abstract description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000007306 functionalization reaction Methods 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 239000002114 nanocomposite Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001556 precipitation 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
- 238000003756 stirring Methods 0.000 claims description 3
- XWJFVXBIWAQFDU-UHFFFAOYSA-N C(CCC)C(CCN)C=1NC=CN=1 Chemical class C(CCC)C(CCN)C=1NC=CN=1 XWJFVXBIWAQFDU-UHFFFAOYSA-N 0.000 claims description 2
- HITBOAGYESUOFH-UHFFFAOYSA-N boric acid hydrochloride Chemical compound Cl.OB(O)O HITBOAGYESUOFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- WJAAARKBHTZZSF-UHFFFAOYSA-N 3-(1h-imidazol-2-yl)butan-1-amine Chemical class NCCC(C)C1=NC=CN1 WJAAARKBHTZZSF-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 150000002118 epoxides Chemical group 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 239000010408 film Substances 0.000 description 14
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910021397 glassy carbon Inorganic materials 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229940090668 parachlorophenol Drugs 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- -1 Chlorophenols compound Chemical class 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 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
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002245 particle Substances 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 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
- 229910052801 chlorine Inorganic materials 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
- 239000000356 contaminant Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 239000002917 insecticide Substances 0.000 description 1
- 238000007689 inspection Methods 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 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
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 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
- 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 an ionic liquid functional composite membrane modified electrode and a preparation method and application thereof to detection of chlorophenol. Special dissolution and high electrical conductivity of ionic liquid are utilized, amino functional ionic liquid conducts epoxide ring-opening on an oxidized graphene-gold nanoparticle composite, the ionic liquid functional graphene-gold nanoparticle composite is prepared, and a dispensing method is adopted to prepare the corresponding composite membrane modified electrode. The surface of the obtained modified electrode has the advantages of being large in effective area and good in dispersibility, and many active sites exist; the synergistic effect of ionic liquid, graphene and gold nanoparticles is played on the aspect of improving direct electrochemistry and electro-catalytic performance, and electrical conductivity and catalytic performance of the modified electrode are improved. An obtained chlorophenol sensor based on the composite membrane modified electrode has the advantages of being low in detection limit, wide in detection range, high in response speed and the like.
Description
Technical field:
The present invention relates to a kind of complex film modified electrode of ion liquid functionalization and its preparation method and application；Specifically
Refer to preparation based on ion liquid functionalization Graphene-gold nanoparticle composite film modified glassy carbon electrode and electrochemistry
Detection application, belongs to field of Environment Protection.
Background technology:
Chlorophenols compound content in water body is the lowest, but pi-electron energy shape on P electronics and phenyl ring in chlorine atom
Become stable π-conjugated systems, major part chlorophenol all to have the biggest toxicity, and can be amassed in biosphere by food chain
Tired, it is difficult to biodegradation, there is " three cause " (carcinogenic, teratogenesis, mutagenesis) effect and genetoxic, be environment
The Typical Representative of middle persistence organic pollutant (Persistent Organic Pollutants, POPs).In water environment
Chlorophenols compound content the lowest, analyze detection there is great difficulty.The most conventional detection method mainly has
Spectrophotography, fluorescence method, HPLC, GC-MS, LC-MS, LC-MS/MS and enzyme-linked immunosorbent assay,
These methods, while have reliable sensitivity and relatively low detection limit, but expensive equipment, sample pretreatment are complicated,
Operate the most numerous and diverse, can not the shortcoming such as Site Detection significantly limit they application [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.].Speed is fast, instrument simple, behaviour because it is analyzed for electrochemical sensing method
Make easy, with low cost, highly sensitive, selectivity is good and can the advantage such as detection in real time, at chlorophenols
The context of detection of compound is applied, as based on ZnSe-CTAB/GCE, HRP/Au/GCE,
The inspection of the electrochemical sensor parachlorophenol of NNH-MWCNTs/GCE, CD/GRs/CPE composite modified electrode
Survey.But at present this type of electrochemical sensor of report mostly exists and such as builds complexity, needs medium or probe, need
Want enzyme " Ping-Pong " and catalysis and parachlorophenol catalysis oxidability difference etc. defect, be highly detrimental to it
Actual application and develop on a large scale.Therefore, find the novel electrode decorative material with high electrocatalysis characteristic,
Develop and still have the biggest challenge for the electrochemical sensor detecting chlorophenol.
Graphene (Grpahene, GR) is the most regularly arranged by monolayer carbon atom, and carbon atom is with sp2Hydridization
It is mutually bonded formation six-membered carbon ring, then extends formation and there is the lamella of cellular two-dimension plane structure (see figure
2), it is the thinnest material with carbon element found in the world at present.GR has low cost, specific surface area is big, heat is steady
Special physics, chemistry and the mechanical performances such as qualitative height, good conductivity, the most in nanoelectronic, sensing
The fields such as device, battery, ultracapacitor and energy storage be widely applied [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 as electrode modified material, due to good electric conductivity and big surface area,
The use of GR nanometer sheet not only increases the modified electrode capture ability to substrate molecule, and promotes its electricity
Son transmission, shows excellent electrocatalysis characteristic.Electrification based on GR modified electrode has been used such as researcher
Learn method for sensing, have detected the phosphoric acid ester insecticide in environment, chlorpromazine, and 4-aminobenzene with sensitivity
Environmental contaminants [Meng X, Yin H, Xu M, Ai S, the Zhu J. such as phenol, catechol, resorcinol and hydroquinone
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.].At present, GR is generally by electronation graphene oxide (GO)
Preparation, but GR is easy to Severe aggregation in chemical reduction procedure, can not really reflect that GR receives
The internal performance of rice monolithic, hinders it significantly as electron transmission performance during electrode modified material.For understanding
Certainly this difficult problem, the most first prepares functional nano-composites with monoatomic layer GO nanometer sheet for substrate, then enters
Row in-situ reducing GO, the GR nano-complex of preparation reduction form, so that GR reaches in composite membrane
The dispersion of molecular level, plays each component in nano composite membrane to greatest extent and improves the synergism of electron transmission.
Golden nanometer particle (AuNPs), in addition to having skin effect and quantum size effect, also has good
Electric conductivity and biocompatibility, can reduce greatly the distance between electron donor and receptor, improve electronics between electrode
Transfer rate, in electrochemical sensing field, there is important application.But AuNPs generally also there will be reunion
Phenomenon, drastically influence it and applies further.Therefore, preparing complex based on AuNPs is to solve this
The important thinking of problem.
Amino functional ionic liquid is not only a kind of high conductivity, is had the green solvent of special solubility property,
And its functional amino can epoxide ring generation ring-opening reaction substantial amounts of with GO surface, modify to based on
The composite material surface of GO/GR.Due to special dissolubility, substantial amounts of electric charge and high electric conductivity, from
The introducing of sub-liquid can be greatly improved the dispersibility of GO/GR sill, stability and electric conductivity.At present,
Use amino functional ionic liquid that GO-AuNPs composite carries out epoxy addition reaction preparation ionic liquid
Body functionalization graphene-gold nano grain complex (IL-GR-AuNPs), and repair based on this complexes membrane
The research of decorations electrode and parachlorophenol context of detection thereof have not been reported.Employing electrostatic assembly and covalency are repaiied by the present invention
Decorations method prepares IL-GR-AuNPs, prepares corresponding modified electrode the detection for parachlorophenol.
Use electrostatic assembly and covalent modification method to prepare IL-GR-AuNPs, GR nanometer sheet pair can not only be made
AuNPs is successfully coated with, the problem that effectively suppression GR nanometer sheet and AuNPs assemble, and improves composite
Specific surface area and electric conductivity, and by the covalent modification of IL, it is also possible to improve leading of complex further
Electrically, dispersibility and stability, give full play to IL, GR and AuNPs advantage in terms of electrode modification,
Compensate for defect when they are used alone.IL-GR-AuNPs complex is used for modified glassy carbon electrode, should
Nano composite membrane can provide more avtive spot, higher electric conductivity and good dispersibility, gives full play to
The synergism of three kinds of components, thus improve tested substance Direct Electrochemistry on modified electrode and electro-catalysis
Performance, to setting up, Novel high-sensitivity electrochemical detection method is significant.
Summary of the invention:
Studying and the demand of application for the deficiencies in the prior art and this area, an object of the present invention is to carry
For a kind of complex film modified electrode of ion liquid functionalization；I.e. by amino functional ionic liquid to graphene oxide
-gold nano grain complex carries out the IL-GR-AuNPs complex that epoxy addition prepares, and with this complex system
Standby corresponding modified electrode.
A kind of complex film modified electrode of ion liquid functionalization provided by the present invention, it is characterised in that described ion
The complex film modified electrode of liquid functionalization is made as basal electrode, ion liquid functionalization composite membrane by glass-carbon electrode
Form for electrode modified material；Described ion liquid functionalization composite membrane is to oxygen by amino functional ionic liquid
Functionalized graphene-gold nano grain complex carries out ion liquid functionalization Graphene-Jenner that epoxy addition prepares
Rice grain complex；Described glass-carbon electrode is designated as GCE；Described graphene oxide is designated as GO, described Graphene
Being designated as GR, described gold nano grain is denoted as AuNPs；Described ionic liquid is 1-methyl-3-aminopropyl imidazoles hydrogen
Bromate, is designated as IL, and its structural formula is as follows:
Described graphene oxide is designated as GO, and described Graphene is designated as GR, and described ionic liquid is 1-butyl-3-
Aminopropyl imidazoles four Chlorine borate, is designated as IL, and its structural formula is as follows:
The two of the purpose of the present invention are to provide the preparation method of the complex film modified electrode of a kind of ion liquid functionalization,
It is characterized in that including step in detail below:
The preparation of (a) AuNPs dispersion liquid
Take the HAuCl that 100mL mass concentration is 0.01%4Aqueous solution, is heated to boiling, is stirred continuously lower slow
The slow 1.5mL mass fraction that adds is the sodium citrate solution of 1%, continues agitating heating and boils 15min, solution
Become aubergine and be cooled to room temperature, recover to original volume with deionized water, obtain AuNPs dispersion liquid；
The preparation of (b) GO-AuNPs nano composite material
Use hummer method to prepare GO, and the GO of a certain amount of gained is dispersed in water so that it is concentration is
5mg/mL, ultrasonic disperse 2 hours, 3000rpm is centrifuged 10min and removes undispersed GO, peeled off
GO dispersion liquid；Take this GO dispersion liquid of 20mL, be stirred continuously down and be slowly added dropwise 10mL's wherein
AuNPs dispersion liquid, is sufficiently mixed under rear room temperature airtight condition stirring 12 hours, and 5000rmp is centrifuged 10min
After, gained brownish black precipitation is GO-AuNPs complex；
The preparation of (c) IL-GR-AuNPs composite
The GO-AuNPs complex 10～40mg weighing gained in step (b) is scattered in 20mL deionized water
In, it is slowly added to supersound process 30min after 5～10mg IL and 5～10mg KOH wherein；After ultrasonic
Dispersion liquid at 80 DEG C heated and stirred backflow 24h, the product 8000rmp obtained be centrifuged 5min, successively
With water and absolute ethanol washing 3 times, gained black solid material is IL-GR-AuNPs complex；
The preparation of the complex film modified glass-carbon electrode of (d) IL-GR-AuNPs
The IL-GR-AuNPs composite deionized water obtained in step (c) is configured to concentration is 1
The pulpous state liquid of mg/mL, takes this pulpous state drop-coated of 6～12 μ L on the surface of glass-carbon electrode, naturally dries,
To IL-GR-AuNPs/GCE modified electrode.
It is characterized in that IL-GR-AuNPs complex described in step (c) be IL in the basic conditions with
In GO-AuNPs complex, the epoxide ring generation open loop on GO molecule generates；Described IL-GR-AuNPs
Complex be IL covalent modification in the AuNPs composite surface being coated with by GR, can with stable existence 2 days,
GO-AuNPs hybrid settles within 10min the most completely, dividing of described IL-GR-AuNPs complex
Dissipate property and stability is significantly improved.
The three of the object of the invention are to provide a kind of complex film modified electrode of ion liquid functionalization in preparation electrochemistry
Application in terms of sensor.Specifically, it is simply that the complex film modified electrode of described ion liquid functionalization is at chlorophenol
The application of context of detection.
More specifically, described chlorophenol is 2,4-Dichlorophenol.
The present invention utilizes the advantage such as solubility property special for IL and high electric conductivity, will by covalent modification method
The IL of amino functional introduces GR-AuNPs hybrid surface, prepares IL-GR-AuNPs complex；Use
Drop-coating is prepared for IL-GR-AuNPs/GCE, and has constructed the third generation based on IL-GR-AuNPs composite membrane
Chlorophenol electrochemical sensor.
Compared with prior art, major advantage is: the complex film modified electrode of gained of the present invention is at electro-catalysis chlorophenol
Aspect has played IL, GR and AuNPs cooperative effect: AuNPs and has improve the specific surface area of composite membrane and lead
Electrically, with entering to inhibit the gathering of GR nanometer sheet；Prepare complex with GR nanometer sheet for substrate, effectively press down
Having made the gathering of AuNPs, both electrostatic assembly improve electro-catalysis and the electron transmission efficiency of complex；IL
Covalent modification further enhancing the electric conductivity of GR-AuNPs hybrid, dispersibility and stability；
IL-GR-AuNPs composite membrane, as the bridge between chlorophenol and basal electrode, substantially increases the capture of parachlorophenol
And electro-catalysis ability.Specifically, the electrochemical catalysis of IL-GR-AuNPs composite membrane parachlorophenol creates expectation
Less than technique effect；The electrocatalytic effect of gained of the present invention complex film modified electrode parachlorophenol, with
Individually AuNPs or GR, or compared with the GR-AuNPs complex obtained by chemical reduction method,
All have and be significantly improved；Sensor of the present invention has that quickly response, Monitoring lower-cut be low, detection range width
And it being applicable to the features such as Site Detection, method is simple to operate, mild condition, preparation cost are low.
Accompanying drawing illustrates:
Fig. 1 is the electron scanning micrograph (b) of embodiment 2 gained IL-GO-AuNPs complex and right
The electron scanning micrograph (a) of ratio 2 gained GO-AuNPs complex.
Fig. 2 is the optics of embodiment 2 gained IL-GO-AuNPs (a) and comparative example 2 gained GO-AuNPs (b)
Photo, the photo of the dispersibility in water when left figure is 0min, right figure is the photograph of the dispersibility after 120min
Sheet.
Fig. 3 is that embodiment 2 (c), comparative example 1 (a), comparative example 2 (b) gained modified electrode are containing 5.0mmol/L
[Fe(CN)6]3-/4-With the cyclic voltammogram in 0.1mol/L KCl solution.
Fig. 4 be IL-GO-AuNPs in embodiment 2 with in the bare electrode in comparative example 1, comparative example 2
GO-AuNPs modified electrode is containing 5.0mmol/L [Fe (CN)6]-3/-4With in 0.1mol/L KCl solution
Impedance diagram.
Fig. 5 is that embodiment 2 (c), comparative example 1 (a), comparative example 2 (b) gained modified electrode are containing
In the PBS buffer solution of the pH=8 of 0.2 μm ol/mL2,4-Dichlorophenol, sweep speed for circulation volt during 100mV/s
Antu.
Fig. 6 is the IL-GO-AuNPs modified electrode PBS buffer solution at pH=8 of gained in embodiment 2
In, sweep speed for 100mV/s time, with 2, the DPV curve that 4-Dichlorophenol concentration constantly increases, illustration for oxidation
Peak current and the linear relationship of 2,4-Dichlorophenol concentration.
Detailed description of the invention:
For being further appreciated by the present invention, the invention will be further described with embodiment below in conjunction with the accompanying drawings, but also
Limit the present invention never in any form.
Embodiment 1:
The preparation of (a) AuNPs dispersion liquid
Take the HAuCl that 100mL mass concentration is 0.01%4Aqueous solution, is heated to boiling, is stirred continuously lower slow
The slow 1.5mL mass fraction that adds is the sodium citrate solution of 1%, continues agitating heating and boils 15min, solution
Become aubergine and be cooled to room temperature, recover to original volume with deionized water, obtain AuNPs dispersion liquid；
The preparation of (b) GO-AuNPs nano composite material
Use hummer method to prepare GO, and the GO of a certain amount of gained is dispersed in water so that it is concentration is
5mg/mL, ultrasonic disperse 2 hours, 3000rpm is centrifuged 10min and removes undispersed GO, peeled off
GO dispersion liquid；Take this GO dispersion liquid of 20mL, be stirred continuously down and be slowly added dropwise 10mL's wherein
AuNPs dispersion liquid, is sufficiently mixed under rear room temperature airtight condition stirring 12 hours, and 5000rmp is centrifuged 10min
After, gained brownish black precipitation is GO-AuNPs complex；
The preparation of (c) IL-GR-AuNPs composite
The GO-AuNPs complex 10mg weighing gained in step (b) is scattered in 20mL deionized water,
It is slowly added to supersound process 30min after 5mg IL and 5mg KOH wherein；By the dispersion liquid after ultrasonic in
At 80 DEG C, heated and stirred backflow 24h, the product 8000rmp obtained are centrifuged 5min, successively by water and anhydrous second
Alcohol washs 3 times, and gained black solid material is IL-GR-AuNPs complex；
The preparation of the complex film modified glass-carbon electrode of (d) IL-GR-AuNPs
The IL-GR-AuNPs composite deionized water obtained in step (c) is configured to concentration is 1
The pulpous state liquid of mg/mL, takes this pulpous state drop-coated of 8 μ L on the surface of glass-carbon electrode, naturally dries, obtain
IL-GR-AuNPs/GCE modified electrode.
Embodiment 2:
The preparation of (a) AuNPs
Prepare according to the method in step (a) in embodiment 1 and condition；
The preparation of (b) GO-AuNPs nano composite material
Prepare according to the method in step (b) in embodiment 1 and condition；
The preparation of (c) IL-GR-AuNPs composite
The GO-AuNPs complex 20mg weighing gained in step (b) is scattered in 20mL deionized water,
It is slowly added to supersound process 30min after 10mg IL and 10mg KOH wherein；By the dispersion liquid after ultrasonic
At 80 DEG C, heated and stirred backflow 24h, the product 8000rmp obtained are centrifuged 5min, successively by water and nothing
Water-ethanol washs 3 times, and gained black solid material is IL-GR-AuNPs complex；
The preparation of (d) IL-GR-AuNPs composite modified glassy carbon electrode
Prepare according to the method in step (d) in embodiment 1 and condition.
Embodiment 3:
The preparation of (a) AuNPs
Prepare according to the method in step (a) in embodiment 1 and condition；
The preparation of (b) GO-AuNPs nano composite material
Prepare according to the method in step (b) in embodiment 1 and condition；
The preparation of (c) IL-GR-AuNPs composite
The GO-AuNPs complex 30mg weighing gained in step (b) is scattered in 20mL deionized water,
It is slowly added to supersound process 30min after 10mg IL and 10mg KOH wherein；By the dispersion liquid after ultrasonic
At 80 DEG C, heated and stirred backflow 24h, the product 8000rmp obtained are centrifuged 5min, successively by water and nothing
Water-ethanol washs 3 times, and gained black solid material is IL-GR-AuNPs complex；
The preparation of (d) IL-GR-AuNPs composite modified glassy carbon electrode
The IL-GR-AuNPs composite deionized water obtained in step (c) is configured to concentration is 1
The pulpous state liquid of mg/mL, takes this pulpous state drop-coated of 10 μ L on the surface of glass-carbon electrode, naturally dries, obtain
IL-GR-AuNPs/ GCE modified electrode.
Embodiment 4:
The preparation of (a) AuNPs
Prepare according to the method in step (a) in embodiment 1 and condition；
The preparation of (b) GO-AuNPs nano composite material
Prepare according to the method in step (b) in embodiment 1 and condition；
The preparation of (c) IL-GR-AuNPs composite
The GO-AuNPs complex 40mg weighing gained in step (b) is scattered in 20mL deionized water,
It is slowly added to supersound process 30min after 10mg IL and 10mg KOH wherein；By the dispersion liquid after ultrasonic
At 80 DEG C, heated and stirred backflow 24h, the product 8000rmp obtained are centrifuged 5min, successively by water and nothing
Water-ethanol washs 3 times, and gained black solid material is IL-GR-AuNPs complex；
The preparation of (d) IL-GR-AuNPs composite modified glassy carbon electrode
Prepare according to the method in step (d) in embodiment 3 and condition.
Comparative example 1:
Directly use naked GCE.
Comparative example 2:
According to the above-mentioned method preparing modified electrode, being prepared as concentration with GO-AuNPs composite is 1
The dispersion liquid of mg/mL, takes 8 μ L drop coatings in the glassy carbon electrode surface of milled, obtains after naturally drying
GO-AuNPs/GCE。
Fig. 1 is the electron scanning micrograph (b) of embodiment 2 gained IL-GR-AuNPs complex and right
The electron scanning micrograph (a) of ratio 2 gained GO-AuNPs complex.Can from scanning electron microscope (a) figure
To find out, as substrate GO nanometer sheet, there is wrinkle striped clearly, the ball of random distribution on its lamella
The AuNPs of shape, its particle diameter is about 100～150nm.After IL covalent modification, IL-GR-AuNPs (figure b) is compound
In thing, the border of AuNPs substantially becomes weak, and the pleated structure of GR nanometer sheet is close to and disappears, complex
The surface of film, compared to the GO-AuNPs of non-IL functionalization, becomes more smooth, and this is primarily due to IL and leads to
Cross the epoxide ring generation ring-opening reaction covalent modification with GO surface to be caused on its surface.
Fig. 2 is the optics of embodiment 2 gained IL-GR-AuNPs (a) and comparative example 2 gained GO-AuNPs (b)
Photo.Left figure is the photo of the dispersibility in water during 0min, and right figure is the dispersibility after 120min
Photo.It can be seen that the product IL-GR-AuNPs after IL functionalization has well dispersion in water
Property, also has no sedimentation after 120min；And the dispersibility that the product GO-AuNPs of non-functionalization is in water
Difference, this covalency being primarily due to IL introduces, and composite surface can be made electrically charged, simultaneously because IL is special
Dissolubility and the existence of amino functional group, make IL-GR-AuNPs complex both have preferable parent
Aqueous, has again charging property, thus has good dispersibility, create condition for preparing modified electrode.
Fig. 3 is that embodiment 2 (c), comparative example 1 (a), comparative example 2 (b) gained modified electrode are containing 5.0mmol/L
[Fe(CN)6]3-/4-With the cyclic voltammogram in 0.1mol/L KCl solution.During in figure, a curve is comparative example 1
Bare electrode is at [Fe (CN)6]3-/4-With the cyclic voltammetry curve in 0.1mol/L KCl solution, b curve comparison in figure
The cyclic voltammetry curve of GO-AuNPs modified electrode in example 2, compared to the GCE in comparative example 1, contrast
The redox current of the GO-AuNPs/GCE in example 2 increases, and this is owing to having high conductivity
After AuNPs Yu GO electrostatic assembly, improve electrode interface to [Fe (CN)6]3-/4-Capture ability, and improve
Electron transmission efficiency between itself and basal electrode.And during in figure, c curve is embodiment 2
GCE in the cyclic voltammetry curve of IL-GR-AuNPs modified electrode, with comparative example 1,2,
GO-AuNPs/GCE compares, and the redox current of IL-GO-AuNPs/GCE is maximum, and this explanation is through altogether
Valency is modified after introducing IL, and IL-GO-AuNPs composite membrane further increases the electrocatalysis characteristic of composite membrane.
Fig. 4 be IL-GR-AuNPs in embodiment 2 with in the bare electrode in comparative example 1, comparative example 2
GO-AuNPs modified electrode is containing 5.0mmol/L [Fe (CN)6]3-/4-With the resistance in 0.1mol/L KCl solution
Anti-figure.It can be seen that spectrogram is divided into two parts, the wherein semicircle correspondence effective electron under high frequency condition
Transfer control process, its half circular diameter represents electron transfer resistance (Ret)；And the linear segment pair of low-frequency range
Answer is that solutes accumulation controls process.Electrochemical impedance result shows, the GO-AuNPs/GCE in comparative example 2
Relative to naked GCE, its arc radius significantly reduces, AuNPs Yu the GO electrostatic assembly of high conductivity is described
After reduce the resistance of electron transmission.The IL-GO-AuNPs/GCE of embodiment 2 correspondence, its arc radius is
Little, it is close in straight line, the covalency of this explanation IL introduces and makes the electric conductivity of IL-GO-AuNPs/GCE enter
One step strengthens, thus shows faster electron transport rate, also illustrate that composite is successfully repaiied simultaneously
Decorations have arrived the surface of electrode.
Fig. 5 is that embodiment 2 (c), comparative example 1 (a), comparative example 2 (b) gained modified electrode are containing 0.2
In the PBS buffer solution of the pH=8 of μm ol/mL2,4-Dichlorophenol, sweep speed for cyclic voltammetric during 100mV/s
Figure.According to figure it can be seen that electrode is containing 2, the PBS of 4-Dichlorophenol only has oxidation peak, explanation
This reaction is irreversible oxidation reaction and electron transfer process.It can be seen that comparative example 1 (curve
A) oxidation peak current of corresponding bare electrode is minimum；GO-AuNPs/GCE electrode corresponding in comparative example 2 (b)
Oxidation peak current significantly increase than the peak current of the bare electrode in comparative example 1；Embodiment 2 is used IL function
The oxidoreduction peak current of the IL-GR-AuNPs/GCE electrode after change is maximum, illustrates to be combined with GO-AuNPs
The electron transport rate of the electrode that material is modified improves, and the electron transport rate of IL-GR-AuNPs/GCE enters
One step increases, and its electric conductivity further enhances, and shows best electrocatalysis characteristic.
Fig. 6 is the IL-GR-AuNPs modified electrode PBS buffer solution at pH=8 of gained in embodiment 2
In, sweep speed for 100mV/s time, with 2, the DPV curve that 4-Dichlorophenol concentration constantly increases, illustration for oxidation
Peak current and the linear relationship of 2,4-Dichlorophenol concentration.Along with 2, the increase of 4-Dichlorophenol concentration, oxidation peak current
It is gradually increased.When 2,4-Dichlorophenol concentration when 0.01～165 μm ol/L, peak current and 2,4-Dichlorophenol concentration
Linear, as shown in illustration in Fig. 6, its linear equation is Ip (μ A)=-1.523C (μm ol/L)
-0.1169 (R=0.9996), detection is limited to 3.3nM.Its performance is much better than GR-AuNPs/GCE (detection range
Being 0.5～48 μm ol/L, detection is limited to 50.6nM).This shows gained in embodiment 2
The 2 of IL-GR-AuNPs modified electrode structure, 4-Dichlorophenol electrochemical sensor has range of linearity width, detection limit
The feature such as low.
Claims (5)
1. the complex film modified electrode of ion liquid functionalization, it is characterised in that described ion liquid functionalization
Complex film modified electrode is by glass-carbon electrode as basal electrode, and ion liquid functionalization composite membrane is as electrode modification
Material forms；Described ion liquid functionalization composite membrane be by amino functional ionic liquid to graphene oxide-
Gold nano grain complex carries out the prepared ion liquid functionalization Graphene-gold nano grain of epoxy addition and is combined
Thing；Described glass-carbon electrode is designated as GCE；Described graphene oxide is designated as GO, and described Graphene is designated as GR,
Described gold nano grain is denoted as AuNPs；Described ionic liquid is 1-methyl-3-aminopropyl imidazoles hydrobromate,
Being designated as IL, its structural formula is as follows:
Described graphene oxide is designated as GO, and described Graphene is designated as GR, and described ionic liquid is 1-butyl-3-
Aminopropyl imidazoles four Chlorine borate, is designated as IL, and its structural formula is as follows:
The preparation method of the complex film modified electrode of described ion liquid functionalization, it is characterised in that include in detail below
Step:
The preparation of (a) AuNPs dispersion liquid
Take the HAuCl that 100mL mass concentration is 0.01%4Aqueous solution, is heated to boiling, is stirred continuously lower slow
The slow 1.5mL mass fraction that adds is the sodium citrate solution of 1%, continues agitating heating and boils 15min, solution
Become aubergine and be cooled to room temperature, recover to original volume with deionized water, obtain AuNPs dispersion liquid；
The preparation of (b) GO-AuNPs nano composite material
Use hummer method to prepare GO, and the GO of a certain amount of gained is dispersed in water so that it is concentration is
5mg/mL, ultrasonic disperse 2 hours, 3000rpm is centrifuged 10min and removes undispersed GO, peeled off
GO dispersion liquid；Take this GO dispersion liquid of 20mL, be stirred continuously down and be slowly added dropwise 10mL's wherein
AuNPs dispersion liquid, is sufficiently mixed under rear room temperature airtight condition stirring 12 hours, and 5000rmp is centrifuged 10min
After, gained brownish black precipitation is GO-AuNPs complex；
The preparation of (c) IL-GR-AuNPs composite
The GO-AuNPs complex 10～40mg weighing gained in step (b) is scattered in 20mL deionized water
In, it is slowly added to supersound process 30min after 5～10mg IL and 5～10mg KOH wherein；After ultrasonic
Dispersion liquid at 80 DEG C heated and stirred backflow 24h, the product 8000rmp obtained be centrifuged 5min, successively
With water and absolute ethanol washing 3 times, gained black solid material is IL-GR-AuNPs complex；
The preparation of the complex film modified glass-carbon electrode of (d) IL-GR-AuNPs
The IL-GR-AuNPs composite deionized water obtained in step (c) is configured to concentration is 1
The pulpous state liquid of mg/mL, takes this pulpous state drop-coated of 6～12 μ L on the surface of glass-carbon electrode, naturally dries,
To IL-GR-AuNPs/GCE modified electrode.
The preparation method of the complex film modified electrode of a kind of ion liquid functionalization the most according to claim 1,
It is characterized in that IL-GR-AuNPs complex described in step (c) be IL in the basic conditions with
In GO-AuNPs complex, the epoxide ring generation open loop on GO molecule generates；Described IL-GR-AuNPs
Complex be IL covalent modification in the AuNPs composite surface being coated with by GR, can with stable existence 2 days,
GO-AuNPs hybrid settles within 10min the most completely, dividing of described IL-GR-AuNPs complex
Dissipate property and stability is significantly improved.
3. a kind of complex film modified electrode of ion liquid functionalization described in claim 1 or 2 is in preparation electrochemistry
Application in terms of sensor.
The application of the complex film modified electrode of a kind of ion liquid functionalization the most according to claim 3, its
It is characterised by that this modified electrode can be used for the detection of chlorophenol.
The application of the complex film modified electrode of a kind of ion liquid functionalization the most according to claim 4, its
It is characterised by that described 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 true CN106018519A (en) | 2016-10-12 |
| CN106018519B CN106018519B (en) | 2019-04-05 |
Family
ID=57110044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610546627.6A Active 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) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107192752A (en) * | 2017-08-01 | 2017-09-22 | 信阳师范学院 | A kind of chemically modified electrode for being used for highly sensitive detection nonyl phenol and preparation method thereof |
| 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 |
| CN109142476A (en) * | 2018-08-14 | 2019-01-04 | 青岛科技大学 | Complex film modified electrode of functionalization molybdenum disulfide nano sheet and preparation method thereof and detection application |
| CN110455895A (en) * | 2019-08-20 | 2019-11-15 | 青岛科技大学 | Graphene oxide/houghite electrochemical DNA biosensor and its preparation method and application of thionine functionalization reduction |
| CN111514930A (en) * | 2020-04-30 | 2020-08-11 | 山东理工大学 | Ionic liquid stable single-atom catalyst and preparation method and application thereof |
| CN112415070A (en) * | 2020-10-27 | 2021-02-26 | 浙江理工大学 | Preparation method of immunosensor modified electrode for silk fibroin detection |
| CN116441555A (en) * | 2023-06-16 | 2023-07-18 | 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 (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120016990A (en) * | 2010-08-17 | 2012-02-27 | 중앙대학교 산학협력단 | Patterning method of graphene using microfluidic systems |
| 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 |
| WO2013123339A1 (en) * | 2012-02-17 | 2013-08-22 | Aksay Ilhan A | Graphene-ionic liquid composites |
| 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 |
| US20150198556A1 (en) * | 2014-01-10 | 2015-07-16 | National Central University | Sensing electrode of enzyme-based sensor and method for manufacturing the same |
| 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 |
| WO2016025532A1 (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 active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120016990A (en) * | 2010-08-17 | 2012-02-27 | 중앙대학교 산학협력단 | Patterning method of graphene using microfluidic systems |
| WO2013123339A1 (en) * | 2012-02-17 | 2013-08-22 | Aksay Ilhan A | Graphene-ionic liquid composites |
| 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 |
| US20150198556A1 (en) * | 2014-01-10 | 2015-07-16 | National Central University | Sensing electrode of enzyme-based sensor and method for manufacturing the same |
| WO2016025532A1 (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 |
| 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 |
Cited By (13)
| 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 |
| CN107192752A (en) * | 2017-08-01 | 2017-09-22 | 信阳师范学院 | A kind of chemically modified electrode for being used for highly sensitive detection nonyl phenol and preparation method thereof |
| 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 |
| 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 |
| CN109142476A (en) * | 2018-08-14 | 2019-01-04 | 青岛科技大学 | Complex film modified electrode of functionalization molybdenum disulfide nano sheet and preparation method thereof and detection application |
| 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 |
| CN110455895A (en) * | 2019-08-20 | 2019-11-15 | 青岛科技大学 | Graphene oxide/houghite electrochemical DNA biosensor and its preparation method and application of thionine functionalization reduction |
| CN111514930A (en) * | 2020-04-30 | 2020-08-11 | 山东理工大学 | Ionic liquid stable single-atom catalyst and preparation method 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 |
| CN112415070A (en) * | 2020-10-27 | 2021-02-26 | 浙江理工大学 | Preparation method of immunosensor modified electrode for silk fibroin detection |
| CN112415070B (en) * | 2020-10-27 | 2022-12-06 | 浙江理工大学 | Preparation method of immunosensor modified electrode for silk fibroin detection |
| CN116441555A (en) * | 2023-06-16 | 2023-07-18 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106018519B (en) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106018519A (en) | Ionic liquid functional composite membrane modified electrode and preparation method and application thereof to detection of chlorophenol | |
| He et al. | Ionic liquid and nanoparticle hybrid systems: Emerging applications | |
| Xu et al. | Unique 3D heterostructures assembled by quasi-2D Ni-MOF and CNTs for ultrasensitive electrochemical sensing of bisphenol A | |
| Xu et al. | Facile synthesis of hierarchical MXene/ZIF-67/CNTs composite for electrochemical sensing of luteolin | |
| Zhao et al. | A novel electrochemical sensor based on 2D CuTCPP nanosheets and platelet ordered mesoporous carbon composites for hydroxylamine and chlorogenic acid | |
| Li et al. | Synthesis of palladium@ gold nanoalloys/nitrogen and sulphur-functionalized multiple graphene aerogel for electrochemical detection of dopamine | |
| Prathap et al. | Simultaneous detection of guanine, adenine, thymine, and cytosine at polyaniline/MnO2 modified electrode | |
| Teymourian et al. | Fe3O4 magnetic nanoparticles/reduced graphene oxide nanosheets as a novel electrochemical and bioeletrochemical sensing platform | |
| Tang et al. | Metal organic framework (ZIF-67)-derived Co nanoparticles/N-doped carbon nanotubes composites for electrochemical detecting of tert-butyl hydroquinone | |
| 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 | |
| Wen et al. | N-doped reduced graphene oxide/MnO2 nanocomposite for electrochemical detection of Hg2+ by square wave stripping voltammetry | |
| Yao et al. | Detection of hydrazine at MXene/ZIF‐8 nanocomposite modified electrode | |
| Pan et al. | Nanocomposite based on graphene and intercalated covalent organic frameworks with hydrosulphonyl groups for electrochemical determination of heavy metal ions | |
| Ma et al. | Non-enzymatic electrochemical hydrogen peroxide sensing using a nanocomposite prepared from silver nanoparticles and copper (II)-porphyrin derived metal-organic framework nanosheets | |
| Lu et al. | Sensitive detection of luteolin based on poly (diallyldimethylammonium chloride)-functionalized graphene-carbon nanotubes hybrid/β-cyclodextrin composite film | |
| Afkhami et al. | Electrochemical determination of levodopa in the presence of ascorbic acid by polyglycine/ZnO nanoparticles/multi-walled carbon nanotubes-modified carbon paste electrode | |
| Hu et al. | Electrochemical detection of rutin with a carbon ionic liquid electrode modified by Nafion, graphene oxide and ionic liquid composite | |
| Chekin et al. | Preparation and characterization of Ni (II)/polyacrylonitrile and carbon nanotube composite modified electrode and application for carbohydrates electrocatalytic oxidation | |
| Sun et al. | Simultaneous electrochemical determination of guanosine and adenosine with graphene–ZrO2 nanocomposite modified carbon ionic liquid electrode | |
| Qi et al. | Novel nonenzymatic hydrogen peroxide sensor based on Fe3O4/PPy/Ag nanocomposites | |
| Keyan et al. | Highly sensitive and selective electrochemical detection of dopamine based on CuCrO2-TiO2 composite decorated screen-printed modified electrode | |
| 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 | |
| Zhe et al. | A screen printed carbon electrode modified with a lamellar nanocomposite containing dendritic silver nanostructures, reduced graphene oxide, and β-cyclodextrin for voltammetric sensing of nitrite | |
| Zhang et al. | Fabrication an electrochemical sensor based on composite of Cu-TCPP nanosheets and PSS functionalized graphene for simultaneous and sensitive determination of dihydroxybenzene isomers |
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 |
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 |
|
| TR01 | Transfer of patent right |