CN109142476B - Functionalized molybdenum disulfide nanosheet composite membrane modified electrode and preparation method and detection application thereof - Google Patents
Functionalized molybdenum disulfide nanosheet composite membrane modified electrode and preparation method and detection application thereof Download PDFInfo
- Publication number
- CN109142476B CN109142476B CN201810922756.XA CN201810922756A CN109142476B CN 109142476 B CN109142476 B CN 109142476B CN 201810922756 A CN201810922756 A CN 201810922756A CN 109142476 B CN109142476 B CN 109142476B
- Authority
- CN
- China
- Prior art keywords
- mos
- aunps
- molybdenum disulfide
- gce
- composite membrane
- 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.)
- Active
Links
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000012528 membrane Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002135 nanosheet Substances 0.000 title claims abstract description 30
- 238000001514 detection method Methods 0.000 title abstract description 18
- 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 62
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002608 ionic liquid Substances 0.000 claims abstract description 21
- 229910052737 gold Inorganic materials 0.000 claims abstract description 15
- 239000010931 gold Substances 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 229910052961 molybdenite Inorganic materials 0.000 claims description 71
- 239000006185 dispersion Substances 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 11
- 239000002114 nanocomposite Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- -1 1-methyl-3- (2' -mercaptoacetyl) propyl imidazole hydrobromide Chemical compound 0.000 claims description 2
- 241001481789 Rupicapra Species 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000243 solution Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 230000027756 respiratory electron transport chain Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000000872 buffer Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000835 electrochemical detection Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- 201000001880 Sexual dysfunction Diseases 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960003887 dichlorophen Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 201000010065 polycystic ovary syndrome Diseases 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 231100000872 sexual dysfunction Toxicity 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 210000001550 testis Anatomy 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Images
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)
Abstract
The invention discloses a functionalized molybdenum disulfide nanosheet composite membrane modified electrode, a preparation method thereof and application of the functionalized molybdenum disulfide nanosheet composite membrane modified electrode in detection of bisphenol A. Stripping molybdenum disulfide in an N, N-dimethylformamide solution containing sulfydryl ionic liquid, stripping the molybdenum disulfide into slices, functionalizing the slices by the ionic liquid, compounding the slices with gold nanoparticles to prepare an ionic liquid-molybdenum disulfide nanosheet-gold nanoparticle compound, and preparing a corresponding composite membrane modified electrode by adopting a dripping coating method. The surface of the modified electrode has the characteristics of large effective area, multiple active sites, good dispersibility and the like, the synergistic effect of the ionic liquid, the molybdenum disulfide nanosheets and the gold nanoparticles is exerted on the aspect of improving the direct electrochemistry and the electrocatalysis performance, and the conductivity and the catalysis performance of the modified electrode are improved. The bisphenol A sensor based on the modified electrode has the advantages of low detection limit, wide detection range, quick response and the like.
Description
The technical field is as follows:
the invention relates to a functionalized molybdenum disulfide nanosheet composite membrane modified electrode and a preparation method and application thereof; in particular to preparation of a glassy carbon electrode modified by an ionic liquid functionalized molybdenum disulfide nanosheet-nanogold composite membrane and application of the glassy carbon electrode in electrochemical detection of bisphenol A, belonging to the field of environmental protection.
Background art:
bisphenol A (BPA) belongs to an exogenous endocrine disrupter and is widely used for synthesizing polycarbonate, epoxy resin and other special additives. Due to its high volume use, BPA readily permeates air, food, water and soil, and thus migrates further into aquatic life and human organs. Research shows that BPA can have adverse effect on the estrogen secretion function of human body, and even if the BPA exists in the blood of human body in low content, the BPA can cause sexual dysfunction, reduce the sperm quality, induce the problems of cardiovascular diseases, polycystic ovary syndrome, recurrent abortion and the like, and various cancers (such as testis, prostate cancer and breast cancer). Therefore, there is an urgent need to develop a simple and sensitive method for detecting BPA. The detection methods commonly used at present comprise gas/liquid chromatography, ultraviolet spectroscopy, fluorescence, surface enhanced Raman scattering, enzyme-linked immunoassay, molecular imprinting and the like. Although these methods have high sensitivity, the practical application is limited due to the expensive instruments, complicated detection process, strong specialization, and the like. The electrochemical analysis method has been widely used for detecting BPA due to the advantages of low cost, simple operation, high sensitivity, rapid analysis and the like, for example, the high-sensitivity detection of BPA has been realized by modified electrodes based on CoTe quantum dots, nitrogen-doped graphene nanosheets, fusion chromophoric acid, AuPd/graphene composites and other functional materials. Although the linear range of BPA detection based on the chemically modified electrode is to be further widened, the detection limit is to be further reduced, and the stability and the sensitivity of the detection method are further improved.
Molybdenum disulfide (MoS)2) Is a natural 2D mineral, often existing in a 2H-type stable structure, with an interior bonded by two layers of sulfur atoms sandwiching a layer of molybdenum atoms, with relatively much weaker inter-layer bonding forces, being bonded against van der waals forces, and with an interlayer spacing of about 0.65 nm. Nanostructured MoS2Has larger specific surface area, can effectively adsorb substances for detection, and can be widely applied to electrochemical detection. However, the layered MoS2Generally, the catalyst exists in a multilayer form, many active sites of the catalyst are deeply buried inside, electrochemical catalytic activity of the catalyst is not fully exerted, and therefore, stripping and recombination are important research directions. Besides surface effect and quantum size effect, gold nanoparticles (AuNPs) also have good conductivity and biocompatibility, can greatly reduce the distance between an electron donor and an electron acceptor, improve the transmission rate of electrons between electrodes, and have important application in the field of electrochemical sensing. However, AuNPs usually have agglomeration phenomenon, which seriously affects further application. Therefore, the preparation of complexes based on AuNPs is an important idea to solve this problem. The sulfhydryl functional ionic liquid is a novel material with high conductivity and special solubility, and the function of the sulfhydryl functional ionic liquidThe thiol group is modified to its surface by forming a gold-sulfur bond with AuNPs. Due to special solubility and high conductivity, the introduction of the ionic liquid can greatly improve the dispersibility, stability and conductivity of the composite material. At present, MoS is treated in a medium containing a sulfhydryl ionic liquid2The ionic liquid functionalized molybdenum disulfide nanosheet-gold nanoparticle composite prepared by stripping and compounding with AuNPs, and preparation of a membrane modified electrode based on the composite and research on BPA detection aspect thereof have not been reported.
The invention content is as follows:
aiming at the defects of the prior art and the requirements of research and application in the field, one of the purposes of the invention is to provide a functionalized molybdenum disulfide nanosheet composite membrane modified electrode; stripping molybdenum disulfide in a medium containing sulfhydryl ionic liquid, compounding with gold nanoparticles to prepare an ionic liquid functionalized molybdenum disulfide nanosheet-gold nanoparticle compound, and preparing a corresponding modified electrode from the compound.
The invention provides a functionalized molybdenum disulfide nanosheet composite membrane modified electrode which is characterized in that a glassy carbon electrode is used as a substrate electrode, and an ionic liquid functionalized molybdenum disulfide nanosheet-gold nanoparticle composite membrane is used as an electrode modification material; the functionalized molybdenum disulfide nanosheet composite membrane is an ionic liquid functionalized molybdenum disulfide nanosheet-gold nanoparticle composite prepared by firstly stripping molybdenum disulfide in an N, N-dimethylformamide solution containing sulfydryl ionic liquid to prepare an ionic liquid functionalized molybdenum disulfide nanosheet dispersion liquid and then compounding the dispersion liquid with gold nanoparticles; the glassy carbon electrode is marked as GCE; the N, N-dimethylformamide is taken as DMF; the molybdenum disulfide nanosheet is marked as MoS2The gold nanoparticles are recorded as AuNPs; the ionic liquid is 1-methyl-3- (2' -mercaptoacetyl) propyl imidazole hydrobromide, is marked as IL, and has the following structural formula:
the invention also aims to provide a preparation method of the functionalized molybdenum disulfide nanosheet composite membrane modified electrode, which is characterized by comprising the following specific steps:
(a)IL-MoS2preparation of the Dispersion
Weighing 10-20 mg IL, adding into 40mL N, N-Dimethylformamide (DMF), and weighing 40mg MoS2Dispersing in the DMF solution, and performing ultrasonic reaction for 12-24 h to obtain IL-MoS2A dispersion liquid;
(b)IL-MoS2preparation of AuNPs nanocomposites
Taking 20mLIL-MoS2Slowly dripping 10mL of AuNPs dispersion liquid into the dispersion liquid under continuous stirring, fully mixing, stirring for 8-18 hours under the closed condition at room temperature, centrifuging for 10min at 5000rmp, washing for 3 times by using water and absolute ethyl alcohol in sequence, and obtaining black precipitate, namely IL-MoS2-AuNPs composite material;
(c)IL-MoS2preparation of-AuNPs composite membrane modified GCE
Polishing the substrate electrode into a mirror surface, and then ultrasonically cleaning and drying by using ultrapure water to obtain the well-treated GCE; subjecting the IL-MoS obtained in step (b) to2Ultrasonically dispersing the AuNPs composite material in deionized water to prepare a dispersion liquid with the concentration of 1mg/mL, dripping 2-20 mu L of the slurry liquid on the surface of the treated GCE, and naturally airing to obtain the IL-MoS2AuNPs/GCE modified electrodes.
Wherein MoS in step (a)2Upon sonication in DMF solution containing IL, MoS is due to the presence of sulfhydryl groups on the IL liquid2Is functionalized by IL while being peeled into a sheet; IL-MoS in step (b)2Complexed with AuNPs via gold-sulfur bonds, IL-MoS2The dispersibility and stability of the AuNPs compound are obviously improved due to the existence of IL; and (c) sequentially polishing the substrate electrode by adopting metallographic abrasive paper and aluminum oxide powder on chamois for polishing, wherein the ultrasonic cleaning time is 30 s.
The invention also aims to provide application of the functionalized molybdenum disulfide nanosheet composite membrane modified electrode in preparation of an electrochemical sensor, and is characterized in that the modified electrode can be used for detection application of bisphenol A.
The invention utilizes the advantages of special solubility and high conductivity of IL to introduce sulfhydryl functionalized IL into MoS by covalent modification method2-AuNPs hybrid surface, preparation of IL-MoS2-AuNPs complex; IL-MoS is prepared by adopting a dropping coating method2AuNPs/GCE, and a third generation BPA electrochemical sensor based on an IL-GR-AuNPs composite membrane is constructed.
Compared with the prior art, the main advantages are that: when the functionalized molybdenum disulfide nanosheet composite membrane is prepared, MoS is firstly subjected to counter-reaction in N, N-dimethylformamide solution containing sulfydryl ionic liquid2Stripping is carried out, MoS due to the presence of thiol groups on the IL liquid2Is peeled into thin sheets and functionalized by IL, and then the dispersion is compounded with AuNPs to prepare IL-MoS2The AuNPs compound has simple preparation method; the functional molybdenum disulfide nanosheet composite membrane modified electrode exerts IL and MoS in the aspect of electrocatalysis of BPA2Synergistic effect of nanosheets and AuNPs: the AuNPs improve the specific surface area and the conductivity of the composite membrane; IL functionalized MoS2The nano-sheet effectively inhibits the aggregation of AuNPs; covalent modification of IL further enhances IL-MoS due to high conductivity and specific solubility2Conductivity, dispersibility and stability of AuNPs composites; IL-MoS2The AuNPs composite membrane is used as a bridge between BPA and a substrate electrode, so that the capture and electrocatalysis capability of BPA is greatly improved, the direct electrochemistry and electrocatalysis performance of a detected substance on a modified electrode are improved, and the AuNPs composite membrane has important significance for establishing a novel high-sensitivity electrochemical detection method.
Description of the drawings:
FIG. 1 shows IL-MoS obtained in comparative example 32Complex (left) and IL-MoS obtained in example 32Scanning electron micrograph of AuNPs complex (right).
FIG. 2 shows IL-MoS modified electrodes obtained in example 3, comparative example 1, comparative example 2 and comparative example 32-AuNPs/GCE(d)、GCE(a)、MoS2(ii)/GCE (b) and IL-MoS2(c) in a solution containing 5.0mmol/L [ Fe (CN)6]3-/4-And cyclic voltammograms in 0.1mol/LKCl solution.
FIG. 3 shows IL-MoS in example 32AuNPs/GCE (d) with GCE (a) in comparative example 1, MoS in comparative example 22IL-MoS in/GCE (b) and comparative example 32(c) in a solution containing 5.0mmol/L [ Fe (CN)6]3-/4-And impedance plots in 0.1mol/LKCl solution.
FIG. 4 shows IL-MoS in example 32AuNPs/GCE vs GCE in comparative example 1, MoS in comparative example 22IL-MoS in/GCE and comparative example 32Cyclic voltammogram at a sweep rate of 100mV/s for/GCE in pH 8 PBS buffer containing 0.2. mu. mol/mL BPA.
FIG. 5A shows the IL-MoS obtained in example 22The DPV curve of the AuNPs/GCE modified electrode, which increases with BPA concentration in PBS buffer solution with pH 8 at a sweep rate of 100mV/s, is shown in FIG. 5B as a linear relationship between oxidation peak current and BPA concentration.
The specific implementation mode is as follows:
for a further understanding of the invention, reference will now be made to the following examples and drawings, which are not intended to limit the invention in any way.
Example 1:
(a)IL-MoS2preparation of the Dispersion
Weighing 10mg IL into 40mL DMF, weighing 40mg MoS2Dispersing in the DMF solution, and performing ultrasonic reaction for 12h to obtain IL-MoS2A dispersion liquid;
(b)IL-MoS2preparation of AuNPs nanocomposites
Taking 20mLIL-MoS2Slowly dripping 10mL AuNPs dispersion solution into the dispersion solution under continuous stirring, stirring for 8 hr under sealed condition at room temperature after fully mixing, centrifuging for 10min at 5000rmp, sequentially washing with water and anhydrous ethanol for 3 times to obtain black precipitate as IL-MoS2-AuNPs composite material;
(c)IL-MoS2preparation of-AuNPs composite membrane modified GCE
Polishing the substrate electrode into a mirror surface, and then ultrasonically cleaning and drying by using ultrapure water to obtain the well-treated GCE; subjecting the IL-MoS obtained in step (b) to2-ultrasound of AuNPs composite materialDispersing in deionized water to obtain 1mg/mL dispersion, applying 5 μ L of the slurry onto the treated GCE surface, and naturally air drying to obtain IL-MoS2AuNPs/GCE modified electrodes.
Example 2:
(a)IL-MoS2preparation of the Dispersion
Weighing 15mg IL into 40mL DMF, and weighing 40mg MoS2Dispersing in the DMF solution, and performing ultrasonic reaction for 16h to obtain IL-MoS2A dispersion liquid;
(b)IL-MoS2preparation of AuNPs nanocomposites
Taking 20mLIL-MoS2Slowly dripping 10mL AuNPs dispersion solution into the dispersion solution under continuous stirring, stirring for 12 hr under sealed condition at room temperature after fully mixing, centrifuging for 10min at 5000rmp, sequentially washing with water and anhydrous ethanol for 3 times to obtain black precipitate as IL-MoS2-AuNPs composite material;
(c)IL-MoS2preparation of-AuNPs composite membrane modified GCE
Polishing the substrate electrode into a mirror surface, and then ultrasonically cleaning and drying by using ultrapure water to obtain the well-treated GCE; subjecting the IL-MoS obtained in step (b) to2Ultrasonically dispersing AuNPs composite material in deionized water to prepare dispersion liquid with the concentration of 1mg/mL, dripping 8 mu L of the slurry on the surface of the treated GCE, and naturally airing to obtain IL-MoS2AuNPs/GCE modified electrodes.
Example 3:
(a)IL-MoS2preparation of the Dispersion
Weighing 20mg IL into 40mL DMF, and weighing 40mg MoS2Dispersing in the DMF solution, and performing ultrasonic reaction for 12h to obtain IL-MoS2A dispersion liquid;
(b)IL-MoS2preparation of AuNPs nanocomposites
Taking 20mLIL-MoS2Slowly dripping 10mL AuNPs dispersion solution into the dispersion solution under continuous stirring, fully mixing, stirring at room temperature under sealed condition for 16 hr, centrifuging at 5000rmp for 10min, sequentially washing with water and anhydrous ethanol for 3 times to obtain black precipitate as IL-MoS2-AuNPs a composite material;
(c)IL-MoS2preparation of-AuNPs composite membrane modified GCE
Polishing the substrate electrode into a mirror surface, and then ultrasonically cleaning and drying by using ultrapure water to obtain the well-treated GCE; subjecting the IL-MoS obtained in step (b) to2Ultrasonically dispersing AuNPs composite material in deionized water to prepare dispersion liquid with the concentration of 1mg/mL, dripping 10 mu L of the slurry liquid on the surface of the treated GCE, and naturally airing to obtain IL-MoS2AuNPs/GCE modified electrodes.
Example 4:
(a)IL-MoS2preparation of the Dispersion
Prepared according to the method and conditions of step (a) in example 3;
(b)IL-MoS2preparation of AuNPs nanocomposites
Taking 20mLIL-MoS2Slowly dripping 10mL AuNPs dispersion solution into the dispersion solution under continuous stirring, fully mixing, stirring at room temperature under sealed condition for 18 hours, centrifuging at 5000rmp for 10min, sequentially washing with water and anhydrous ethanol for 3 times to obtain black precipitate as IL-MoS2-AuNPs composite material;
(c)IL-MoS2preparation of-AuNPs composite membrane modified GCE
Polishing the substrate electrode into a mirror surface, and then ultrasonically cleaning and drying by using ultrapure water to obtain the well-treated GCE; subjecting the IL-MoS obtained in step (b) to2Ultrasonically dispersing AuNPs composite material in deionized water to prepare dispersion liquid with the concentration of 1mg/mL, dripping 12 mu L of the slurry on the surface of the treated GCE, and naturally airing to obtain IL-MoS2AuNPs/GCE modified electrodes.
Example 5:
(a)IL-MoS2preparation of the Dispersion
Prepared according to the method and conditions in step (a) of example 3;
(b)IL-MoS2preparation of AuNPs nanocomposites
Prepared according to the method and conditions in step (b) of example 3;
(c)IL-MoS2-AuNPs composite membrane modificationPreparation of GCE
Polishing the substrate electrode into a mirror surface, and then ultrasonically cleaning and drying by using ultrapure water to obtain the well-treated GCE; subjecting the IL-MoS obtained in step (b) to2Ultrasonically dispersing AuNPs composite material in deionized water to prepare dispersion liquid with the concentration of 1mg/mL, dripping 16 mu L of the slurry on the surface of the treated GCE, and naturally airing to obtain IL-MoS2AuNPs/GCE modified electrodes.
Comparative example 1:
the naked GCE was used directly.
Comparative example 2:
according to the method for preparing the modified electrode, MoS is used2The nano-sheet is ultrasonically dispersed to prepare a dispersion liquid with the concentration of 1mg/mL, 10 mu L of dispersion liquid is dripped on the ground GCE surface, and the MoS is obtained after natural airing2/GCE。
Comparative example 3:
according to the above method for preparing a modified electrode, using IL-MoS2The compound is prepared into dispersion liquid with the concentration of 1mg/mL, 10 mu L of the dispersion liquid is dripped on the ground GCE surface, and IL-MoS is obtained after natural airing2/GCE。
FIG. 1 shows IL-MoS obtained in comparative example 32Complex (left) and IL-MoS obtained in example 32Scanning electron micrograph of AuNPs complex (right). As can be seen from the figure, IL-MoS2Is in a sheet stacking structure, the size of the sheet is less than 100nm, and when the sheet is compounded with AuNPs, the IL-MoS2The AuNPs are in a spherical structure, and the surface of the spherical AuNPs is coated with IL-MoS2Nanosheets, demonstrating successful preparation of IL-MoS2-AuNPs。
FIG. 2 shows a modified electrode IL-MoS prepared in example 3 of the present invention2The AuNPs/GCE is a working electrode, the saturated calomel electrode is a reference electrode, and the platinum wire electrode is a counter electrode; for comparison, GCE and MoS obtained in comparative example 1, comparative example 2 and comparative example 3 were used2(ii)/GCE and IL-MoS2The working electrode is/GCE, which contains 5.0mmol/L of [ Fe (CN)6]3-/4-And cyclic voltammograms in 0.1mol/L KCl solution. As is evident from the figure, the voltammetric response of the bare GCE (curve a) is minimal when modified with MoS2When nano sheet is used (curved)Line b), an increase in redox current, indicating MoS2Nanosheet enhanced [ Fe (CN)6]3-/4-Transfer at the electrode surface; IL-MoS2the/GCE (curve c) shows a further increased voltammetric signal, indicating that the introduction of IL can improve the electrochemical performance of the modified electrode; and IL-MoS2AuNPs/GCE (curve d) then exhibits the maximum redox peak current, which states IL-MoS after introduction of IL2AuNPs fully develop IL and MoS2And the advantages of three components of AuNPs, and the electrocatalytic performance of the modified electrode is further increased through the synergistic effect of the three components.
FIG. 3 shows IL-MoS in example 32AuNPs/GCE vs GCE in comparative example 1, MoS in comparative example 22IL-MoS in/GCE and comparative example 32The solution of/GCE in a solution containing 5.0mmol/L [ Fe (CN)6]3-/4-And impedance plot in 0.1mol/L KCl solution. As can be seen from the figure, the spectrum is divided into two parts, where a semicircle under high frequency corresponds to the effective electron transfer control process, and the diameter of the semicircle represents the electron transfer resistance (Ret); while the linear part of the lower frequency band corresponds to the solute diffusion control process. Electrochemical impedance results show that the MoS of comparative example 22The arc radius of the/GCE (curve b) is significantly reduced compared to the bare GCE (curve a), indicating that MoS2Nanosheet reduced [ Fe (CN)6]3-/4-Resistance to electron transfer with the substrate electrode. IL-MoS2The smaller electrochemical impedance is given by/GCE (curve c), which shows that the introduction of IL improves the conductivity of the modified electrode and accelerates the electrochemical reaction; example 3 corresponding IL-MoS2Minimum radius of the arc of AuNPs/GCE (curve d), also indicating IL-MoS2The AuNPs composite membrane improves the conductivity of the modified electrode and increases the effective active area and active sites thereof through the synergistic effect of the components, thereby showing the fastest electron transfer rate.
FIG. 4 shows IL-MoS in example 32AuNPs/GCE vs GCE in comparative example 1, MoS in comparative example 22IL-MoS in/GCE and comparative example 32Cyclic voltammogram at a sweep rate of 100mV/s for/GCE in pH 8 PBS buffer containing 0.2. mu. mol/mL BPA. It can be seen from the figure thatThe electrode had only an oxidation peak in PBS buffer containing BPA, indicating that the reaction is an irreversible oxidation reaction and electron transfer process. As can be seen from the graph, the oxidation peak current of GCE corresponding to comparative example 1 (curve a) is the smallest; corresponding MoS in comparative example 22The oxidation peak current of/GCE (curve b) is significantly increased compared to the peak current of the bare electrode in comparative example 1; corresponding IL-MoS in comparative example 32The oxidation peak current of/GCE (curve c) is further increased; IL-MoS in example 32Maximum redox peak current of AuNPs/GCE (curve d), indicating the use of IL-MoS2The electron transfer rate of the electrode modified by the composite material is improved, and BPA is in IL-MoS after the electrode is compounded with AuNPs2Maximum oxidation peak current of AuNPs/GCE, indicating BPA passage through IL-MoS2The AuNPs modified film further increases the electron transfer rate with the substrate electrode, and shows extremely high electrocatalytic performance to BPA.
FIG. 5A shows the IL-MoS obtained in example 22The DPV curve of the AuNPs/GCE modified electrode, which increases with BPA concentration in PBS buffer solution with pH 8 at a sweep rate of 100mV/s, is shown in FIG. 5B as a linear relationship between oxidation peak current and BPA concentration. The oxidation peak current gradually increased with increasing 2, 4-dichlorophen concentration. As shown in fig. 5B, when the concentration of BPA is 0.005-50 μmol/L, the peak current and the concentration of BPA have a two-stage linear relationship, and the linear equations are Ip (μ a) ═ 0.003C (μmol/L) +0.260(R ═ 0.998) and Ip (μ a) ═ 0.162C (μmol/L) +0.116(R ═ 0.995), respectively, and the detection limit is 1.5 nM.
Table 1 shows the IL-MoS of the modified electrode of the present invention2Comparison of the Performance of AuNPs/GCE for detection of BPA with other electroanalytical methods
As can be seen from Table 1, the IL-MoS according to the invention was used2After the AuNPs nano composite modifies the substrate electrode, the detection range of the AuNPs nano composite for BPA is obviously enlarged compared with that of the existing modified electrode, the detection limit is obviously reduced, and the result shows that the IL-MoS2the-AuNPs nano composite membrane modified electrode has better electrocatalytic oxidation effect on BPA, so thatAnd better stability and sensitivity are shown.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. A functionalized molybdenum disulfide nanosheet composite membrane modified electrode is characterized in that a glassy carbon electrode is used as a substrate electrode, and an ionic liquid functionalized molybdenum disulfide nanosheet-gold nanoparticle composite membrane is used as an electrode modification material; the functionalized molybdenum disulfide nanosheet composite membrane is an ionic liquid functionalized molybdenum disulfide nanosheet-gold nanoparticle composite prepared by firstly stripping molybdenum disulfide in an N, N-dimethylformamide solution containing sulfydryl ionic liquid to prepare an ionic liquid functionalized molybdenum disulfide nanosheet dispersion liquid and then compounding the dispersion liquid with gold nanoparticles; the glassy carbon electrode is marked as GCE; the N, N-dimethylformamide is taken as DMF; the molybdenum disulfide nanosheet is marked as MoS2The gold nanoparticles are recorded as AuNPs; the ionic liquid is 1-methyl-3- (2' -mercaptoacetyl) propyl imidazole hydrobromide, is marked as IL, and has the following structural formula:
the preparation method of the functionalized molybdenum disulfide nanosheet composite membrane modified electrode is characterized by comprising the following specific steps of:
(a)IL-MoS2preparation of the Dispersion
Weighing 10-20 mg of IL, adding into 40mL of DMF, and weighing 40mg of MoS2Dispersing in the DMF solution, and performing ultrasonic reaction for 12-24 h to obtain IL-MoS2A dispersion liquid;
(b)IL-MoS2preparation of AuNPs nanocomposites
Taking 20mLIL-MoS2Slowly dripping 10mL of AuNPs dispersion liquid into the dispersion liquid under continuous stirring, fully mixing, stirring for 8-18 hours under the closed condition at room temperature, centrifuging at 5000rpm for 10min, sequentially washing for 3 times by using water and absolute ethyl alcohol, and obtaining black precipitate, namely IL-MoS2-AuNPs composite material;
(c)IL-MoS2preparation of-AuNPs composite membrane modified GCE
Polishing the substrate electrode into a mirror surface, and then ultrasonically cleaning and drying by using ultrapure water to obtain the well-treated GCE; subjecting the IL-MoS obtained in step (b) to2Ultrasonically dispersing the AuNPs composite material in deionized water to prepare a dispersion liquid with the concentration of 1mg/mL, dripping 2-20 mu L of the dispersion liquid on the surface of the treated GCE, and naturally airing to obtain the IL-MoS2AuNPs/GCE modified electrodes.
2. The functionalized molybdenum disulfide nanosheet composite membrane modified electrode of claim 1, wherein in step (a) of the preparation method, MoS is added2Upon sonication in DMF solution containing IL, MoS is due to the presence of sulfhydryl groups on the IL liquid2Is functionalized by IL while being peeled into a sheet; IL-MoS in step (b)2Complexed with AuNPs via gold-sulfur bonds, IL-MoS2The dispersibility and stability of the AuNPs compound are obviously improved due to the existence of IL; and (c) sequentially polishing the substrate electrode by adopting metallographic abrasive paper and aluminum oxide powder on chamois for polishing, wherein the ultrasonic cleaning time is 30 s.
3. The application of the functionalized molybdenum disulfide nanosheet composite membrane modified electrode in the preparation of electrochemical sensors according to claim 1 or 2, wherein the modified electrode can be used for detecting bisphenol A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810922756.XA CN109142476B (en) | 2018-08-14 | 2018-08-14 | Functionalized molybdenum disulfide nanosheet composite membrane modified electrode and preparation method and detection application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810922756.XA CN109142476B (en) | 2018-08-14 | 2018-08-14 | Functionalized molybdenum disulfide nanosheet composite membrane modified electrode and preparation method and detection application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109142476A CN109142476A (en) | 2019-01-04 |
| CN109142476B true CN109142476B (en) | 2020-07-07 |
Family
ID=64793347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810922756.XA Active CN109142476B (en) | 2018-08-14 | 2018-08-14 | Functionalized molybdenum disulfide nanosheet composite membrane modified electrode and preparation method and detection application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109142476B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110124700B (en) * | 2019-06-11 | 2022-06-21 | 吉林师范大学 | Dual-functional MoS2Application of/ZnO composite material in bisphenol A trace detection |
| CN112526120B (en) * | 2020-11-19 | 2024-05-14 | 山东省农业科学院农业质量标准与检测技术研究所 | Method for detecting salbutamol based on SPR technology |
| CN115060774B (en) * | 2022-06-08 | 2023-04-11 | 华南理工大学 | Preparation method and application of glycerol enzyme-free sensor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103412021A (en) * | 2013-08-29 | 2013-11-27 | 青岛科技大学 | Functionalized ionic liquid-hydrotalcite-like composite material fixed protein modified electrode as well as preparation method and application thereof |
| CN105784807A (en) * | 2015-11-28 | 2016-07-20 | 青岛科技大学 | Ionic liquid covalent-modified graphene-hydrotalcite-like composite membrane fixed protein-modified electrode, and preparation method and detection application thereof |
| CN106018519A (en) * | 2016-07-12 | 2016-10-12 | 青岛科技大学 | Ionic liquid functional composite membrane modified electrode and preparation method and application thereof to detection of chlorophenol |
| CN106442666A (en) * | 2016-08-11 | 2017-02-22 | 青岛科技大学 | Ionic liquid functional carbon nitride nanosheet modified electrode as well as preparation and application of electrode in chlorphenol detection |
-
2018
- 2018-08-14 CN CN201810922756.XA patent/CN109142476B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103412021A (en) * | 2013-08-29 | 2013-11-27 | 青岛科技大学 | Functionalized ionic liquid-hydrotalcite-like composite material fixed protein modified electrode as well as preparation method and application thereof |
| CN105784807A (en) * | 2015-11-28 | 2016-07-20 | 青岛科技大学 | Ionic liquid covalent-modified graphene-hydrotalcite-like composite membrane fixed protein-modified electrode, and preparation method and detection application thereof |
| CN106018519A (en) * | 2016-07-12 | 2016-10-12 | 青岛科技大学 | Ionic liquid functional composite membrane modified electrode and preparation method and application thereof to detection of chlorophenol |
| CN106442666A (en) * | 2016-08-11 | 2017-02-22 | 青岛科技大学 | Ionic liquid functional carbon nitride nanosheet modified electrode as well as preparation and application of electrode in chlorphenol detection |
Non-Patent Citations (4)
| Title |
|---|
| Bingjie Xu et al.A novel electrochemical quercetin sensor based on Pd/MoS2-ionic liquid functionalized ordered mesoporous carbon.《Electrochimica Acta》.2017,第247卷657-665. * |
| Electrochemical determination of 2,4-dichlorophenol by using a glassy carbon electrode modified with molybdenum disulfide, ionic liquid and gold/silver nanorods;Huayu Huang et al;《Microchimica Acta》;20180510;第185卷;292 * |
| YayunYang et al.Electrochemical non-enzyme sensor for detecting clenbuterol(CLB) based on MoS2-Au-PEI-hemin layered nanocomposites.《Biosensors and Bioelectronics》.2016,第89卷461-467. * |
| 一步法制备单层二硫化钼纳米片;肖林平 等;《广东化工》;20160630;第43卷(第12期);46-47 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109142476A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Priya et al. | A novel voltammetric sensor for the simultaneous detection of Cd2+ and Pb2+ using graphene oxide/κ-carrageenan/l-cysteine nanocomposite | |
| Amani et al. | Electrochemical immunosensor for the breast cancer marker CA 15–3 based on the catalytic activity of a CuS/reduced graphene oxide nanocomposite towards the electrooxidation of catechol | |
| Zhou et al. | Fabrication and characterization of highly sensitive and selective sensors based on porous NiO nanodisks | |
| Song et al. | Sandwich-type electrochemical immunosensor for CEA detection using magnetic hollow Ni/C@ SiO2 nanomatrix and boronic acid functionalized CPS@ PANI@ Au probe | |
| Azzouz et al. | Advances in functional nanomaterial-based electrochemical techniques for screening of endocrine disrupting chemicals in various sample matrices | |
| Promsuwan et al. | Flow injection amperometric nitrite sensor based on silver microcubics-poly (acrylic acid)/poly (vinyl alcohol) modified screen printed carbon electrode | |
| CN109142476B (en) | Functionalized molybdenum disulfide nanosheet composite membrane modified electrode and preparation method and detection application thereof | |
| Mulaba-Bafubiandi et al. | A voltammetric carbon paste sensor modified with NiO nanoparticle and ionic liquid for fast analysis of p-nitrophenol in water samples | |
| Dong et al. | Exploiting multi-function metal-organic framework nanocomposite Ag@ Zn-TSA as highly efficient immobilization matrixes for sensitive electrochemical biosensing | |
| Zhou et al. | Preparation of a gold electrode modified with Au–TiO 2 nanoparticles as an electrochemical sensor for the detection of mercury (II) ions | |
| CN106018519B (en) | The application of complex film modified electrode of ion liquid functionalization and preparation method thereof and detection chlorophenol | |
| Han et al. | A novel sandwich-type immunosensor for detection of carcino-embryonic antigen using silver hybrid multiwalled carbon nanotubes/manganese dioxide | |
| Hasanzadeh et al. | Ultrasensitive immunoassay of tumor protein CA 15.3 in MCF-7 breast cancer cell lysates and unprocessed human plasma using gold nanoparticles doped on the structure of mesoporous silica | |
| Huang et al. | Morphology-controlled electrochemical sensing of environmental Cd2+ and Pb2+ ions on expanded graphite supported CeO2 nanomaterials | |
| Kumar et al. | Nanostructured palladium-reduced graphene oxide platform for high sensitive, label free detection of a cancer biomarker | |
| Yu et al. | Amperometric determination of nitrite by using a nanocomposite prepared from gold nanoparticles, reduced graphene oxide and multi-walled carbon nanotubes | |
| Yang et al. | Facile synthesis of silver nanoparticle-decorated graphene oxide nanocomposites and their application for electrochemical sensing | |
| Gao et al. | A label-free electrochemical immunosensor for carcinoembryonic antigen detection on a graphene platform doped with poly (3, 4-ethylenedioxythiophene)/Au nanoparticles | |
| Yang et al. | Molecularly imprinted electrochemical sensor based on the synergic effect of nanoporous gold and copper nanoparticles for the determination of cysteine | |
| Zhao et al. | Employing the interfacial barrier of P-rGO/ZnO microspheres for improving the electrochemical sensing performance to dopamine | |
| Lei et al. | Gold nanoparticles decorated bimetallic CuNi-based hollow nanoarchitecture for the enhancement of electrochemical sensing performance of nitrite | |
| CN115112744A (en) | Electrochemical sensor and preparation method and application thereof | |
| Mei et al. | A sensitive and selective electrochemical sensor for the simultaneous determination of trace Cd 2+ and Pb 2+ | |
| Yin et al. | Self-calibrating electrochemical sensors based on uniformly dispersed Ag nanoclusters in nitrogen-doped carbon sheets for determination of nitrite | |
| Tchekep et al. | Alternative approach for highly sensitive and free-interference electrochemical dopamine sensing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231121 Address after: 518000, No. 301A, 3rd Floor, Building 6, Hongxin Industrial Park, No. 1303, Sightseeing Road, Dabuxiang Community, Guanlan Street, Longhua District, Shenzhen City, Guangdong Province Patentee after: SHENZHEN JIENENGDA INDUSTRIAL Co.,Ltd. Address before: No. 53, Zhengzhou Road, North District, Qingdao, Shandong Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY |