CN109142476A - Complex film modified electrode of functionalization molybdenum disulfide nano sheet and preparation method thereof and detection application - Google Patents
Complex film modified electrode of functionalization molybdenum disulfide nano sheet and preparation method thereof and detection application Download PDFInfo
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 96
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 31
- 239000002135 nanosheet Substances 0.000 title claims abstract description 22
- 238000001514 detection method Methods 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 57
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000010931 gold Substances 0.000 claims abstract description 14
- 229910052737 gold Inorganic materials 0.000 claims abstract description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002608 ionic liquid Substances 0.000 claims abstract description 5
- 229910052961 molybdenite Inorganic materials 0.000 claims description 54
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 46
- 239000002131 composite material Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- -1 sulfhydryl ion Chemical class 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002242 deionisation method Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000002114 nanocomposite Substances 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 241001481789 Rupicapra Species 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010985 leather Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 229940106691 bisphenol a Drugs 0.000 abstract description 25
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000001548 drop coating Methods 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 238000000034 method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000005611 electricity Effects 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
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- 230000035945 sensitivity Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- KJUCPVIVNLPLEE-UHFFFAOYSA-N 2,6-difluoro-n-[2-fluoro-5-[5-[2-[(6-morpholin-4-ylpyridin-3-yl)amino]pyrimidin-4-yl]-2-propan-2-yl-1,3-thiazol-4-yl]phenyl]benzenesulfonamide Chemical compound S1C(C(C)C)=NC(C=2C=C(NS(=O)(=O)C=3C(=CC=CC=3F)F)C(F)=CC=2)=C1C(N=1)=CC=NC=1NC(C=N1)=CC=C1N1CCOCC1 KJUCPVIVNLPLEE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001568 sexual effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 208000008899 Habitual abortion Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 210000001672 ovary Anatomy 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 208000034213 recurrent susceptibility to 1 pregnancy loss Diseases 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses the applications of a kind of complex film modified electrode of functionalization molybdenum disulfide nano sheet and preparation method thereof and detection bisphenol-A.First in the N containing sulfhydryl ion liquid, molybdenum disulfide is removed in dinethylformamide solution, by ion liquid functionalization while molybdenum disulfide is stripped into thin slice, again with the compound obtained ionic liquid-molybdenum disulfide nano sheet-gold nano grain compound of gold nano grain, corresponding complex film modified electrode is prepared for using drop-coating.Gained modified electrode surface has the characteristics that effective area is big, active site is more, good dispersion, the synergistic effect that ionic liquid, molybdenum disulfide nano sheet 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.Bisphenol-A sensor of the gained based on the 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 a kind of complex film modified electrodes of functionalization molybdenum disulfide nano sheet and its preparation method and application；Tool
Body refers to based on the preparation of ion liquid functionalization molybdenum disulfide nano sheet-nanogold complex film modified glass-carbon electrode and electrochemistry inspection
Bisphenol-A application is surveyed, environment protection field is belonged to.
Background technique:
Bisphenol-A (BPA) belongs to a kind of exogenous incretion interferent, is widely used in polycarbonate synthesis, epoxy resin also
There are other specialist additives.Due to largely using, BPA is easily penetrated into air, food, water and soil, to further move
It moves on in aquatile and human organ.Studies have shown that BPA can generate adverse effect to human body estrogen secretion function, even if
There is lower content to be present in blood of human body, may also lead to sex dysfunction, reduce sperm quality, induces cardiovascular disease, more
The problems such as capsule Ovary Syndrome, recurrent miscarriage and various cancers (such as testis, prostate cancer and breast cancer).Therefore, it is badly in need of
Develop a kind of easy, sensitive BPA detection method.Currently used detection method includes gas phase and liquid phase chromatography, ultraviolet spectra
Method, fluorescence method, Surface enhanced Raman scattering method, enzyme-linked immunosorbent assay and molecular imprinting method etc..Although these method sensitivity
It is higher, but since instrument is more expensive, detection process is comparatively laborious, it is in addition professional very strong the features such as limit in fact
Border application.Electrochemical analysis method has been used extensively due to the advantages that its inexpensive, easy to operate, high sensitivity, quick analysis
In detection BPA, such as based on CoTe quantum dot, nitrogen-doped graphene nanometer sheet, fusion color acid, AuPd/ graphene complex and its
The modified electrode of his functional material has been achieved with the highly sensitive detection to BPA.Although based on chemically modified electrode detection BPA's
The range of linearity up for further widening, detection limit up for further decreasing, further increase detection method stability and
Sensitivity.
Molybdenum disulfide (MoS2) it is a kind of natural 2D mineral, often with the presence of 2H type rock-steady structure, inside is by two layers of sulphur
Atom is mingled with one layer of molybdenum atom and is bonded, and binding force between layers will be much weaker in contrast, be located against model
What De Huali was combined, interlamellar spacing is about 0.65nm.The MoS of nanostructure2With biggish specific surface area, can effectively adsorb
Substance is detected, therefore can be widely applied to Electrochemical Detection.But stratiform MoS2Usually exist with multilayer form,
Many active sites are deeply buried in inside, and electrochemical catalysis activity is not given full play to, therefore, remove and it is compound be it
Important research direction.Gold nanoparticle (AuNPs) also has good other than with skin effect and quantum size effect
Electric conductivity and biocompatibility, can reduce greatly electron donor between receptor at a distance from, improve electronics in interelectrode transmission rate,
There is important application in electrochemical sensing field.But AuNPs generally also will appear agglomeration, drastically influence it further
Using.Therefore, compound of the preparation based on AuNPs is the important thinking for solving the problems, such as this.Thiol-functionalized ionic liquid is
A kind of high conductivity, the new material with special solubility property, functional group sulfydryl are repaired by forming golden sulfide linkage with AuNPs
Adorn its surface.Due to special dissolubility and high electric conductivity, the introducing of ionic liquid can greatly improve composite material
Dispersibility, stability and electric conductivity.Currently, to MoS in the medium containing sulfhydryl ion liquid2Removed, then with AuNPs
It is compound to prepare ion liquid functionalization molybdenum disulfide nano sheet-gold nano grain compound, and modified based on the complexes membrane
Electrode preparing and its having not been reported to the research of BPA context of detection.
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 functionalization molybdenum disulfide nano sheet；I.e. in the medium containing sulfhydryl ion liquid to molybdenum disulfide into
Row removing, then with gold nano grain is compound prepares ion liquid functionalization molybdenum disulfide nano sheet-gold nano grain compound,
And corresponding modified electrode is prepared with the compound.
A kind of complex film modified electrode of functionalization molybdenum disulfide nano sheet provided by the present invention, it is characterised in that the function
The complex film modified electrode of molybdenum disulfide nano sheet can be changed by glass-carbon electrode as basal electrode, ion liquid functionalization molybdenum disulfide
Nanometer sheet-gold nanoparticle composite membrane is as electrode modified material；The functionalization molybdenum disulfide nano sheet composite membrane is first to exist
Molybdenum disulfide is removed in n,N-Dimethylformamide solution containing sulfhydryl ion liquid, prepares ion liquid functionalization
Molybdenum disulfide nano sheet dispersion liquid, then the dispersion liquid again with the compound ion liquid functionalization curing obtained of gold nano grain
Molybdenum nanometer sheet-gold nano grain compound；The glass-carbon electrode is denoted as GCE；The N,N-dimethylformamide is denoted as DMF；Institute
It states molybdenum disulfide nano sheet and is denoted as MoS2, the gold nano grain is denoted as AuNPs；The ionic liquid is 1- methyl -3- (2 ' -
Mercaptoacetyl) propyl imidazole hydrobromate, it is denoted as IL, structural formula is as follows:
The second object of the present invention is to provide a kind of preparation side of complex film modified electrode of functionalization molybdenum disulfide nano sheet
Method, it is characterised in that comprising the following specific steps
(a)IL-MoS2The preparation of dispersion liquid
It weighs 10~20mg IL to be added in 40mL n,N-Dimethylformamide (DMF), then weighs 40mg MoS2It is scattered in
In above-mentioned DMF solution, ultrasonic reaction 12~for 24 hours, obtain IL-MoS2Dispersion liquid；
(b)IL-MoS2The preparation of-AuNPs nanocomposite
Take 20mLIL-MoS2Dispersion liquid is stirred continuously down the AuNPs dispersion liquid that 10mL is slowly added dropwise thereto, sufficiently mixed
Room temperature stirs 8~18 hours under confined conditions after conjunction, after 5000rmp is centrifuged 10min, is successively washed 3 times with water and dehydrated alcohol,
Gained black precipitate is IL-MoS2- AuNPs composite material；
(c)IL-MoS2The preparation of the complex film modified GCE of-AuNPs
By basal electrode sanding and polishing at mirror surface, then the GCE that must be handled well after dry with ultrapure water ultrasonic cleaning；By step
(b) IL-MoS obtained in2- AuNPs compound material ultrasound is scattered in deionization, is configured to the dispersion that concentration is 1mg/mL
Liquid takes 2~20 μ L pulpous state drop-coated on the surface GCE handled well, obtains IL-MoS after natural drying2- AuNPs/GCE modification
Electrode.
Wherein MoS in step (a)2When ultrasonic in the DMF solution containing IL, due to the presence of sulfydryl on IL liquid, MoS2
By IL functionalization while being stripped into thin slice；IL-MoS in step (b)2Compound, the IL-MoS that passes through golden sulfide linkage with AuNPs2-
Due to the presence of IL in AuNPs compound, dispersibility and stability are significantly improved；Basal electrode in step (c)
Using the alumina powder on abrasive paper for metallograph and chamois leather, successively sanding and polishing, the time of ultrasonic cleaning are 30s to sanding and polishing.
It is electrochemical in preparation that the three of the object of the invention are to provide a kind of complex film modified electrode of functionalization molybdenum disulfide nano sheet
Learn the application in terms of sensor, it is characterised in that the modified electrode can be used for the detection application of bisphenol-A.
The present invention utilizes the advantages that special solubility property of IL and high electric conductivity, by covalent modification method by sulfydryl function
The IL of energyization introduces MoS2- AuNPs hybrid surface, is prepared for IL-MoS2- AuNPs compound；IL- is prepared for using drop-coating
MoS2- AuNPs/GCE, and constructed the third generation BPA electrochemical sensor based on IL-GR-AuNPs composite membrane.
Compared with prior art, major advantage is: the compound film preparation of functionalization molybdenum disulfide nano sheet of the present invention
When first in the N,N-dimethylformamide solution containing sulfhydryl ion liquid to MoS2It is removed, due to sulfydryl on IL liquid
Presence, MoS2By IL functionalization while being stripped into thin slice, then the dispersion liquid again with the compound obtained IL-MoS of AuNPs2-
AuNPs compound, preparation method are simple；The complex film modified electrode of functionalization molybdenum disulfide nano sheet is in the electro-catalysis side BPA
Face has played IL, MoS2Nanometer sheet and AuNPs synergistic effect: AuNPs improves the specific surface area and electric conductivity of composite membrane；IL
The MoS of functionalization2Nanometer sheet effectively inhibits the aggregation of AuNPs；Due to high electric conductivity and special dissolubility, IL's is covalently repaired
Decorations further enhance IL-MoS2Electric conductivity, dispersibility and the stability of-AuNPs compound； IL-MoS2- AuNPs composite membrane
As the bridge between BPA and basal electrode, the capture and electro-catalysis ability to BPA are substantially increased, to improve detected material
Direct Electrochemistry and electrocatalysis characteristic of the matter on modified electrode, to establish novel high-sensitivity electrochemical detection method have it is important
Meaning.
Detailed description of the invention:
Fig. 1 is 3 gained IL-MoS of comparative example23 gained IL-MoS of compound (left side) and embodiment2- AuNPs compound (right side)
Electron scanning micrograph.
Fig. 2 is embodiment 3,3 gained modified electrode IL-MoS of comparative example 1, comparative example 2 and comparative example2-AuNPs/GCE
(d)、GCE(a)、MoS2/ GCE (b) and IL-MoS2/ GCE (c) is containing 5.0 mmol/L [Fe (CN)6]3-/4-And 0.1mol/L
Cyclic voltammogram in KCl solution.
Fig. 3 is the IL-MoS in embodiment 32In GCE (a), comparative example 2 in-AuNPs/GCE (d) and comparative example 1
MoS2IL-MoS in/GCE (b) and comparative example 32/ GCE (c) is containing 5.0mmol/L [Fe (CN)6]3-/4-And 0.1mol/L
Impedance diagram in KCl solution.
Fig. 4 is the IL-MoS in embodiment 32GCE, the MoS in comparative example 2 in-AuNPs/GCE and comparative example 12/GCE
With the IL-MoS in comparative example 32/ GCE in the PBS buffer solution of the pH=8 containing 0.2 μm of ol/mL BPA, sweep speed and be
Cyclic voltammogram when 100mV/s.
Fig. 5 A is IL-MoS obtained in embodiment 22The PBS buffer solution of-AuNPs/GCE modified electrode in pH=8
In, sweep speed be 100mV/s when, the DPV curve constantly increased with BPA concentration, Fig. 5 B is the line of oxidation peak current Yu BPA concentration
Sexual intercourse.
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)IL-MoS2The preparation of dispersion liquid
It weighs 10mg IL to be added in 40mL DMF, then weighs 40mg MoS2It is scattered in above-mentioned DMF solution, ultrasonic reaction
12h obtains IL-MoS2Dispersion liquid；
(b)IL-MoS2The preparation of-AuNPs nanocomposite
Take 20mLIL-MoS2Dispersion liquid is stirred continuously down the AuNPs dispersion liquid that 10mL is slowly added dropwise thereto, sufficiently mixed
Room temperature stirs 8 hours under confined conditions after conjunction, after 5000rmp is centrifuged 10min, successively washs 3 times with water and dehydrated alcohol, gained
Black precipitate is IL-MoS2- AuNPs composite material；
(c)IL-MoS2The preparation of the complex film modified GCE of-AuNPs
By basal electrode sanding and polishing at mirror surface, then the GCE that must be handled well after dry with ultrapure water ultrasonic cleaning；By step
(b) IL-MoS obtained in2- AuNPs compound material ultrasound is scattered in deionization, is configured to the dispersion that concentration is 1mg/mL
Liquid takes the 5 μ L pulpous state drop-coated on the surface GCE handled well, obtains IL-MoS after natural drying2- AuNPs/GCE modification electricity
Pole.
Embodiment 2:
(a)IL-MoS2The preparation of dispersion liquid
It weighs 15mg IL to be added in 40mL DMF, then weighs 40mg MoS2It is scattered in above-mentioned DMF solution, ultrasonic reaction
16h obtains IL-MoS2Dispersion liquid；
(b)IL-MoS2The preparation of-AuNPs nanocomposite
Take 20mLIL-MoS2Dispersion liquid is stirred continuously down the AuNPs dispersion liquid that 10mL is slowly added dropwise thereto, sufficiently mixed
Room temperature stirs 12 hours under confined conditions after conjunction, after 5000rmp is centrifuged 10min, is successively washed 3 times with water and dehydrated alcohol, institute
Obtaining black precipitate is IL-MoS2- AuNPs composite material；
(c)IL-MoS2The preparation of the complex film modified GCE of-AuNPs
By basal electrode sanding and polishing at mirror surface, then the GCE that must be handled well after dry with ultrapure water ultrasonic cleaning；By step
(b) IL-MoS obtained in2- AuNPs compound material ultrasound is scattered in deionization, is configured to the dispersion that concentration is 1mg/mL
Liquid takes the 8 μ L pulpous state drop-coated on the surface GCE handled well, obtains IL-MoS after natural drying2- AuNPs/GCE modification electricity
Pole.
Embodiment 3:
(a)IL-MoS2The preparation of dispersion liquid
It weighs 20mg IL to be added in 40mL DMF, then weighs 40mg MoS2It is scattered in above-mentioned DMF solution, ultrasonic reaction
12h obtains IL-MoS2Dispersion liquid；
(b)IL-MoS2The preparation of-AuNPs nanocomposite
Take 20mLIL-MoS2Dispersion liquid is stirred continuously down the AuNPs dispersion liquid that 10mL is slowly added dropwise thereto, sufficiently mixed
Room temperature stirs 16 hours under confined conditions after conjunction, after 5000rmp is centrifuged 10min, is successively washed 3 times with water and dehydrated alcohol, institute
Obtaining black precipitate is IL-MoS2- AuNPs composite material；
(c)IL-MoS2The preparation of the complex film modified GCE of-AuNPs
By basal electrode sanding and polishing at mirror surface, then the GCE that must be handled well after dry with ultrapure water ultrasonic cleaning；By step
(b) IL-MoS obtained in2- AuNPs compound material ultrasound is scattered in deionization, is configured to the dispersion that concentration is 1mg/mL
Liquid takes the 10 μ L pulpous state drop-coated on the surface GCE handled well, obtains IL-MoS after natural drying2- AuNPs/GCE modification electricity
Pole.
Embodiment 4:
(a)IL-MoS2The preparation of dispersion liquid
According to the method and condition preparation of step (a) in embodiment 3；
(b)IL-MoS2The preparation of-AuNPs nanocomposite
Take 20mLIL-MoS2Dispersion liquid is stirred continuously down the AuNPs dispersion liquid that 10mL is slowly added dropwise thereto, sufficiently mixed
Room temperature stirs 18 hours under confined conditions after conjunction, after 5000rmp is centrifuged 10min, is successively washed 3 times with water and dehydrated alcohol, institute
Obtaining black precipitate is IL-MoS2- AuNPs composite material；
(c)IL-MoS2The preparation of the complex film modified GCE of-AuNPs
By basal electrode sanding and polishing at mirror surface, then the GCE that must be handled well after dry with ultrapure water ultrasonic cleaning；By step
(b) IL-MoS obtained in2- AuNPs compound material ultrasound is scattered in deionization, is configured to the dispersion that concentration is 1mg/mL
Liquid takes the 12 μ L pulpous state drop-coated on the surface GCE handled well, obtains IL-MoS after natural drying2- AuNPs/GCE modification electricity
Pole.
Embodiment 5:
(a)IL-MoS2The preparation of dispersion liquid
According to the method and condition preparation in step (a) in embodiment 3；
(b)IL-MoS2The preparation of-AuNPs nanocomposite
According to the method and condition preparation in step (b) in embodiment 3；
(c)IL-MoS2The preparation of the complex film modified GCE of-AuNPs
By basal electrode sanding and polishing at mirror surface, then the GCE that must be handled well after dry with ultrapure water ultrasonic cleaning；By step
(b) IL-MoS obtained in2- AuNPs compound material ultrasound is scattered in deionization, is configured to the dispersion that concentration is 1mg/mL
Liquid takes the 16 μ L pulpous state drop-coated on the surface GCE handled well, obtains IL-MoS after natural drying2- AuNPs/GCE modification electricity
Pole.
Comparative example 1:
Directly use naked GCE.
Comparative example 2:
According to the above-mentioned method for preparing modified electrode, MoS is used2It is 1 mg/mL's that nanometer sheet ultrasonic disperse, which is prepared into concentration,
Dispersion liquid takes 10 μ L drop coatings on the surface GCE of milled, obtains MoS after natural drying2/GCE。
Comparative example 3:
According to the above-mentioned method for preparing modified electrode, IL-MoS is used2Compound is prepared into the dispersion that concentration is 1mg/mL
Liquid takes 10 μ L drop coatings on the surface GCE of milled, obtains IL-MoS after natural drying2/GCE。
Fig. 1 is 3 gained IL-MoS of comparative example23 gained IL-MoS of compound (left side) and embodiment2- AuNPs compound (right side)
Electron scanning micrograph.It can be seen from the figure that IL-MoS2The size of packed structures in the form of sheets, piece is less than 100nm,
After compound with AuNPs, IL-MoS2- AuNPs is rendered as chondritic, and the spherical surface AuNPs is coated with IL-MoS2Nanometer sheet,
Proof is successfully prepared IL-MoS2-AuNPs。
Fig. 2 is the modified electrode IL-MoS prepared with the embodiment of the present invention 32- AuNPs/GCE is working electrode, is saturated sweet
Mercury electrode is reference electrode, and platinum electrode is to electrode；As a comparison, resulting with comparative example 1, comparative example 2 and comparative example 3
GCE、MoS2/ GCE and IL-MoS2/ GCE is working electrode, is containing 5.0 mmol/L [Fe (CN)6]3-/4-And 0.1mol/LKCl
Cyclic voltammogram in solution.From the graph, it is apparent that naked GCE (volt-ampere of curve a) respond it is minimum, when being modified with MoS2
(curve b), redox current increase, and illustrate MoS when nanometer sheet2Nanometer sheet improves [Fe (CN)6]3-/4-In electrode surface
Transmitting； IL-MoS2(curve c) shows the voltammetric signal further increased to/GCE, shows that the introducing of IL can be improved and repairs
Adorn the chemical property of electrode；And IL-MoS2- AuNPs/GCE (curve d) then presents maximum redox peak current, this
It says after introducing IL, IL-MoS2- AuNPs has given full play to IL, MoS2With the advantage of tri- kinds of components of AuNPs, pass through their collaboration
Effect further increases the electrocatalysis characteristic of modified electrode.
Fig. 3 is the IL-MoS in embodiment 32GCE, the MoS in comparative example 2 in-AuNPs/GCE and comparative example 12/GCE
With the IL-MoS in comparative example 32/ GCE is containing 5.0mmol/L [Fe (CN)6]3-/4-With the impedance in 0.1mol/L KCl solution
Figure.It can be seen from the figure that spectrogram is divided into two parts, wherein the semicircle under high frequency condition corresponds to effective electronics transfer and controlled
Journey, half circular diameter represent electronics transfer resistance (Ret)；And it is that solutes accumulation controlled that the linear segment of low-frequency range is corresponding
Journey.Electrochemical impedance is the results show that MoS in comparative example 22(curve b) is relative to naked GCE (curve a), arc radius by/GCE
It significantly reduces, illustrates MoS2Nanometer sheet reduces [Fe (CN)6]3-/4-The resistance of electron transmission between basal electrode.IL-MoS2/
(curve c) provides smaller electrochemical impedance to GCE, shows that the introducing of IL improves the electric conductivity of modified electrode, accelerates electrification
Learn reaction；The corresponding IL-MoS of embodiment 32(arc radius of curve d) is minimum, equally illustrates IL-MoS by-AuNPs/GCE2-
AuNPs composite membrane improves the electric conductivity of modified electrode by the synergistic effect of each component, increase its effective active area and
Active site, thus show most fast electron transport rate.
Fig. 4 is the IL-MoS in embodiment 32GCE, the MoS in comparative example 2 in-AuNPs/GCE and comparative example 12/GCE
With the IL-MoS in comparative example 32/ GCE in the PBS buffer solution of the pH=8 containing 0.2 μm of ol/mL BPA, sweep speed and be
Cyclic voltammogram when 100mV/s.According to figure as can be seen that electrode only has oxidation peak, explanation in the PBS buffer solution containing BPA
The reaction is irreversible oxidation reaction and electron transfer process.It can be seen from the figure that (curve a) is corresponding for comparative example 1
The oxidation peak current of GCE is minimum；Corresponding MoS in comparative example 22(oxidation peak current of curve b) is than naked in comparative example 1 by/GCE
The peak current of electrode significantly increases；Corresponding IL-MoS in comparative example 32(oxidation peak current of curve c) further increases/GCE；
IL-MoS in embodiment 32(the redox peak current of curve d) is maximum, illustrates to use IL-MoS by-AuNPs/GCE2Composite material
After the electron transport rate of the electrode of modification improves, and it is compound with AuNPs, BPA is in IL-MoS2The oxidation peak of-AuNPs/GCE
Electric current is maximum, shows that BPA passes through IL-MoS2- AuNPs modified membrane, the electron transport rate between basal electrode further increase
Greatly, the electrocatalysis characteristic high to BPA is shown.
Fig. 5 A is IL-MoS obtained in embodiment 22The PBS buffer solution of-AuNPs/GCE modified electrode in pH=8
In, sweep speed be 100mV/s when, the DPV curve constantly increased with BPA concentration, Fig. 5 B is the line of oxidation peak current Yu BPA concentration
Sexual intercourse.With the increase of 2,4- Dichlorophenol concentration, oxidation peak current is gradually increased.As shown in Figure 5 B, when BPA concentration exists
When 0.005~50 μm of ol/L, peak current and BPA concentration are in two sections of linear relationships, linear equation be respectively Ip (μ A)=
0.003C (μm ol/L)+0.260 (R=0.998) and Ip (μ A)=0.162C (μm ol/L)+0.116 (R=0.995), detection
It is limited to 1.5nM.
Table 1 is modified electrode IL-MoS of the present invention2- AuNPs/GCE detects BPA performance and other electricity analytical methods
Compare
As can be seen from Table 1, using IL-MoS of the present invention2After-AuNPs nano-complex modifies basal electrode,
The detection range of BPA is significantly increased compared with existing modified electrode, detection limit significantly reduces, and illustrates IL-MoS2-AuNPs
Nano combined film modified electrode has better electrocatalytic oxidation effect to BPA, thus shows better stability and spirit
Sensitivity.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent conversion regime, be included within the scope of the present invention.
Claims (3)
1. a kind of complex film modified electrode of functionalization molybdenum disulfide nano sheet, it is characterised in that the functionalization molybdenum disulfide nano
The complex film modified electrode of piece is by glass-carbon electrode as basal electrode, ion liquid functionalization molybdenum disulfide nano sheet-Jenner's grain of rice
Sub- composite membrane is as electrode modified material；The functionalization molybdenum disulfide nano sheet composite membrane is first to contain sulfhydryl ion liquid
N,N-Dimethylformamide solution in molybdenum disulfide is removed, prepare ion liquid functionalization molybdenum disulfide nano sheet point
Dispersion liquid, then the dispersion liquid again with the compound ion liquid functionalization molybdenum disulfide nano sheet-gold nano obtained of gold nano grain
Particle composites；The glass-carbon electrode is denoted as GCE；The N,N-dimethylformamide is denoted as DMF；The molybdenum disulfide nano sheet
It is denoted as MoS2, the gold nano grain is denoted as AuNPs；The ionic liquid is 1- methyl -3- (2 '-mercaptoacetyl) propyl miaow
Azoles hydrobromate is denoted as IL, and structural formula is as follows:
The preparation method of the complex film modified electrode of functionalization molybdenum disulfide nano sheet, it is characterised in that including walking in detail below
It is rapid:
(a)IL-MoS2The preparation of dispersion liquid
It weighs 10~20mg IL to be added in 40mL DMF, then weighs 40mg MoS2It is scattered in above-mentioned DMF solution, ultrasonic reaction
12~for 24 hours, obtain IL-MoS2Dispersion liquid；
(b)IL-MoS2The preparation of-AuNPs nanocomposite
Take 20mLIL-MoS2Dispersion liquid is stirred continuously down the AuNPs dispersion liquid that 10mL is slowly added dropwise thereto, is sufficiently mixed rear chamber
Temperature stirs 8~18 hours under confined conditions, after 5000rpm is centrifuged 10min, is successively washed 3 times with water and dehydrated alcohol, gained is black
Color precipitating is IL-MoS2- AuNPs composite material；
(c)IL-MoS2The preparation of the complex film modified GCE of-AuNPs
By basal electrode sanding and polishing at mirror surface, then the GCE that must be handled well after dry with ultrapure water ultrasonic cleaning；By step (b)
Obtained in IL-MoS2- AuNPs compound material ultrasound is scattered in deionization, is configured to the dispersion liquid that concentration is 1mg/mL, is taken
2~20 μ L pulpous state drop-coated obtains IL-MoS on the surface GCE handled well after natural drying2- AuNPs/GCE modified electrode.
2. a kind of preparation method of complex film modified electrode of functionalization molybdenum disulfide nano sheet according to claim 1,
It is characterized in that MoS in step (a)2When ultrasonic in the DMF solution containing IL, due to the presence of sulfydryl on IL liquid, MoS2It is shelled
By IL functionalization while from flakiness；IL-MoS in step (b)2Compound, the IL-MoS that passes through golden sulfide linkage with AuNPs2- AuNPs is multiple
The presence in object due to IL is closed, dispersibility and stability are significantly improved；The sanding and polishing of basal electrode in step (c)
Using the alumina powder on abrasive paper for metallograph and chamois leather, successively sanding and polishing, the time of ultrasonic cleaning are 30s.
3. a kind of complex film modified electrode of functionalization molybdenum disulfide nano sheet as claimed in claim 1 or 2 is preparing electrochemical sensing
Application in terms of device, it is characterised in that the modified electrode can be used for the detection of bisphenol-A.
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