CN108845010A - Ionic liquid auxiliary synthesis of carbon/molybdenum disulfide and graphene oxide composite material are for detecting chloramphenicol - Google Patents

Abstract

The present invention provides a kind of composite material, a kind of modified electrode, a kind of electrochemical sensor and applications for measuring chloramphenicol for assisting obtaining platelike molybdenumdisulfide and graphene oxide based on ionic liquid.It is characterized by scanning electron microscope, transmission electron microscope, Raman spectrum and X-ray diffraction pattern and structure to composite material, electrochemical Characterization is carried out by cyclic voltammetry and electrochemical impedance spectroscopy, shows good chemical property and electro-catalysis ability.The sensor has good stability, and repeatability and reproducibility can be used for eye drops, the measurement of chloramphenicol in milk and urine sample.

Description

Ionic liquid assists synthesis of carbon/molybdenum disulfide with graphene oxide composite material for detecting Chloramphenicol

Technical field

The present invention relates to advanced composite material (ACM)s, in particular it relates to which a kind of assist obtaining de-layer based on ionic liquid The advanced composite material (ACM) of shape molybdenum disulfide and graphene oxide, and highly sensitive electrochemical sensor and measurement chloramphenicol Using.

Background technique

It is removed from graphite from graphene success, the research of stratiform two dimension (two-dimension, 2D) nano material is prominent to fly Push ahead vigorously [1].Similar to 2D stratified nano materials molybdenum disulfide (the Molybdenum disulfide, MoS of graphene₂), due to Its excellent nanoelectronics, photoelectronics, catalysis and collection of energy performance and be concerned [2,3].

Currently used for preparing 2D MoS₂Method mainly include mechanical dissociation, ion insertion removing and liquid phase stripping method.Its In, liquid phase stripping method is green, easy and efficient [4].This method is with ultrasonic wave added solvent and 2D MoS₂Between it is mutual Effect is to overcome the interaction of the Van der Waals force between material bodies layer, to remove 2D MoS₂Nanometer sheet.But since material exists It may reunite in drying process, so being difficult to control MoS₂The number of plies [5].

For ionic liquid (Ionic liquid, IL) since its steam forces down, electrochemical stability is high, ionic conductivity height and The features such as stability is high [6] is applied not only to supporting electrolyte [7], is also used for electrode modification.In recent years, IL has been used for replacing For toxic liquid, the extensive synthesis [8,9] of 2D material is prepared by grinding.The armaticity of IL can effectively break model moral Hua Li [10-12] removes stratiform MoS to obtain₂.However, ion is inserted into stripping method poor reproducibility, the nanometer sheet specification of preparation is larger [7].Therefore, MoS₂Nanometer sheet it is efficient, high quality and simple preparation are still challenge.

Graphene oxide (Graphene oxide, GO) is widely used in electrochemistry due to its significant electrochemical properties Application in Sensing.Compared with graphite or graphene, MoS₂Electronic conductivity it is lower [13], therefore MoS₂Hybrid material with GO can It can overcome this defect.Further, since MoS₂There is similar form and layer structure with both GO, so MoS₂It is miscellaneous with GO Changing material may cause improved structural compatibility and electrochemical properties [14].

Chloramphenicol (Chloramphenicol, CAP) be for treating the broad spectrum antimicrobial agent of zoonosis [15-17], but Excess intake CAP may result in serious toxic side effect [18-20] from food or drug.Currently, the technology master of detection CAP It to include high performance liquid chromatography [21] that reverse phase injects chromatography [22], gas chromatography-mass spectrum [23], liquid chromatography-mass spectrography [24] Deng.These traditional analysis methods need the experimentation of expensive equipment and complexity, and electrochemical method is because of simplicity, cost It is low, the features such as high sensitivity, receive more and more attention.The most of related nano material synthetic methods reported at present Complexity is related to noxious material [25-27], therefore green, sensitively prepares electrochemical sensor and still needs to explore.

Summary of the invention

(1) technical problems to be solved

Since material may reunite in the drying process, so MoS₂The number of plies be difficult to control.Ion insertion removing The nanometer sheet specification of method poor reproducibility, preparation is larger, therefore, MoS₂Nanometer sheet it is efficient, high quality and simple preparation are still this Field urgent problem.In addition, green, sensitively prepare electrochemical sensor and still need to this field and go to explore and solve.

(2) technical solution

To solve the above problems, the present invention provides the following technical solutions：

On the one hand, the present invention provides the composite material of a kind of molybdenum disulfide based on ionic liquid and graphene oxide, It is characterized in that：The composite material has formula MoS₂-IL/GO。

In one embodiment, the IL is 1- butyl -3- methyl imidazolium tetrafluoroborate [BMIM] BF₄.However, appointing What suitable IL may be used to the present invention, and the present invention is not limited to 1- butyl -3- methyl imidazolium tetrafluoroborates.

Another aspect prepares the molybdenum disulfide and graphene oxide above-mentioned based on ionic liquid the present invention provides a kind of Composite material method, which is characterized in that described method includes following steps：

(1) by MoS₂It is moved in DMF with IL, ultrasound 15 hours；

(2) substance of step (1) is added into GO, and mixture is 30 minutes ultrasonic again at room temperature；

(3) it is centrifuged, black object is washed with water and is dispersed again in DMF, obtain MoS₂- IL/GO nanocomposite.

Preferably, the IL is 1- butyl -3- methyl imidazolium tetrafluoroborate [BMIM] BF₄。

Another aspect, the present invention provides a kind of modified electrodes, it is characterised in that：The modified electrode is based on above-mentioned The molybdenum disulfide of ionic liquid and the composite material of graphene oxide are modified.

In one embodiment, the modified electrode is modified glass-carbon electrode.However, any suitable electrode all may be used With for the present invention, the present invention is not limited to glass-carbon electrodes.

Another aspect, the present invention provides a kind of electrochemical sensors, it is characterised in that：The electrochemical sensor includes Mentioned-above glass-carbon electrode.

In another aspect, the present invention provides mentioned-above electrochemical sensors to detect the application in chloramphenicol.

Preferably, the detection of the detection is limited to 0.047 μm of olL^-1。

In some embodiments, the application is the measurement of chloramphenicol in milk and urine sample for eye drops.

(3) effective effect

By green, efficient method has synthesized one kind and has assisted obtaining stratiform based on ionic liquid present inventor The advanced composite material (ACM) of molybdenum disulfide and graphene oxide, and the electrochemical sensor measurement for developing a kind of high sensitivity Chloramphenicol (CAP) obtains significant technical effect, specific as follows：

(1) preparation method is simple, efficient；By scanning electron microscope, transmission electron microscope, Raman spectrum and X are penetrated Line diffraction characterizes the pattern and structure of synthetic material, as a result confirms MoS₂The synthesis of-IL/GO.

(2) electrochemical Characterization is carried out by cyclic voltammetry and electrochemical impedance spectroscopy, is prepared with the present invention novel MoS₂The glass-carbon electrode (Glassy carbon electrode, GCE) of-IL/GO composite modification shows excellent electrification Learn performance and electro-catalysis ability.

(3) at optimum conditions, the high sensitivity measuring to CAP may be implemented in electrochemical sensor of the invention, detection Range is wide, and detection limits low, favorable reproducibility, and stability is good, and shows good chemical property when detecting actual sample.? Under conditions of optimization, sensor is in 0.1-400 μm of olL^-1Linear with current-responsive value under CAP concentration, detection is limited to 0.047 μmol·L^-1, and it is used successfully to eye drops, the measurement of CAP in milk and urine sample.

Detailed description of the invention

In conjunction with the drawings and specific embodiments, the present invention will be described in detail, and practical range of the invention is not limited with this.

Fig. 1 is MoS₂(A)、MoS₂- IL (B), GO (C) and MoS₂The SEM of-IL/GO (D, E) schemes, MoS₂- IL/GO's (F) TEM figure.

Fig. 2 is MoS₂、MoS₂- IL and MoS₂The Raman spectrogram (A) and XRD diagram (B) of-IL/GO.

Fig. 3 is modified electrode in 200 μm of olL^-1CV in the PBS (pH 7) of CAP schemes (A), sweep speed 100mV s^-1；Modified electrode is in 5mmolL^-1Fe(CN)₆ ^3-/4-0.1molL^-1The EIS of KCl schemes (B).Naked GCE (a), MoS₂/GCE (b), MoS₂- IL/GCE (c), GO/GCE (d) and MoS₂-IL/GO/GCE(e)。

Fig. 4 is different modifying volume (A) and pH (C) in MoS₂200 μm of olL are detected on-IL/GO/GCE^-1The DPV of CAP Curve；The relationship (B) of peak current intensity and modification volume, the linear relationship (D) of pH and spike potential.

It is 200 μm of olL that (A) is schemed in Fig. 5^-1CAP is in 0.1molL^-1MoS in PBS (pH 7)₂The CV of-IL/GO/GCE is bent Line (a)；Figure (B) is the linear relationship between peak current and sweep speed.

Fig. 6 is 0.1-400 μm of olL^-1CAP (A) and 0.1-10 μm of olL^-1CAP (B) is in MoS₂On-IL/GO/GCE Calibration curve between DPV curve and peak current intensity and CAP concentration.a-m：0.1,0.5,1,3,7,10,20,40,60, 80,100,150,200,300,400 μm of olL^-1CAP。

Specific embodiment

The present invention is further described combined with specific embodiments below.Raw materials used and equipment is this field in embodiment Technical staff is known, and is that can buy or be easy to get or be made in the market.

One, embodiment is prepared

1. reagent and instrument

GO(>99%, Nanjing Ji Cang nanosecond science and technology Co., Ltd)；MoS₂(99%, Sigma-Aldrich), [BMIM] BF₄ (97%, Shanghai Mike's woods biochemical technology Co., Ltd)；N,N-Dimethylformamide (DMF,>99.5%, Shanghai Mike woods is biochemical Science and Technology Ltd.) and CAP (>=98%, Beijing Hua Maike biotechnology Co., Ltd).The chemical reagent used is It analyzes pure.

Use S-4800 (Hitachi, Japan) scanning electron microscope (Scanning electron microscope, SEM) With JEM-2100F (Electronics Co., Ltd, Japan) transmission electron microscope (Transmission electron Microscope, TEM) carry out surface morphology research.Measurement X- is penetrated in D/max-2600PC (Co., Ltd. Neo-Confucianism, Japan) Line diffraction (X-ray diffraction, XRD), measures Raman spectrum in Invia-reflex (Reinshaw, Britain). CHI760E electrochemical workstation (Shanghai Chen Hua Instrument Ltd., China), by Ag/AgCl (saturation KCl) as reference electricity Pole, the conventional three-electrode system that platinum column is formed as auxiliary electrode, modified GCE as working electrode.

2.MoS₂The preparation of-IL/GO nanocomposite

MoS₂- IL composite material is using ultrasonic wave removing preparation.By 40mg MoS₂With 200 μ LIL ([BMIM] BF₄) move to In 40mL DMF, ultrasound 15 hours.Then to 1mL GO (1gL^-1) in be added 1mL MoS₂-IL(1g·L^-1), and will mixing Object is 30 minutes ultrasonic again at room temperature.After centrifugation, black object is washed with water and is dispersed again in DMF to obtain MoS₂-IL/ GO nanocomposite.MoS is prepared when IL is not added in an identical manner₂As control.

3. the preparation of modified GCE

The surface GCE is polished with 0.2-0.5 μm of alumina powder, then uses ethyl alcohol and water washing.By 3 μ LMoS₂- IL/GO is multiple Object drop is closed on preparatory clean GCE and is dried at room temperature for prepare modified electrode.MoS is prepared in a similar manner₂, MoS2- IL and GO modified GCE is as control.

Two, effect example

1.MoS₂The characterization of-IL/GO

As shown in Figure 1, MoS₂(Figure 1A), MoS₂- IL (Figure 1B), GO (Fig. 1 C) and MoS₂- IL/GO's (Fig. 1 D, Fig. 1 E) SEM image shows surface appearance feature.Fig. 1 D and Fig. 1 E shows, MoS₂Piece is evenly dispersed on the surface of GO sheet material.Such as Shown in Fig. 1 F, MoS₂The TEM image of-IL/GO shows several MoS₂Thin slice be stacked and with GO sheet interconnections.The result shows that MoS₂It is sufficiently mixed with GO, effectively increases the surface area of synthetic material.

As shown in Fig. 2, Fig. 2A depicts the Raman spectrum of synthetic material.MoS₂In 375.8cm^-1And 402.9cm^-1Place's display Main Raman active peak, corresponds respectively to MoS₂The E of crystal¹ _2gAnd A_1g.With MoS₂It compares, MoS₂- IL and MoS₂- IL/GO allusion quotation Type E¹ _2gAnd A_1gThe intensity at peak is due to MoS₂Go layer structure, and be dispersed in the surface GO [28] and substantially reduce.In addition, MoS₂- IL and MoS₂The E of-IL/GO¹ _2gAnd A_1gPeak position is subjected to displacement, wherein the A of MoS2-IL_1gThe position at peak is moved to 401.3cm^-1.The result shows that IL can effectively break MoS₂Van der Waals force between piece removes stratiform MoS to obtain₂。MoS₂-IL/ The Raman spectrum of GO is in 1353.2cm^-1And 1585.3cm^-1(I_D/I_G=0.88) D the and G band for showing GO at respectively, is attributed to Local defect/unordered and sp²Carbonization structure.

To further characterize prepared material, Fig. 2 B shows MoS₂、MoS₂- IL and MoS₂The XRD diagram of-IL/GO.It can It observes, MoS₂Main peak appears in 14.3 °, reflects (002) face, and in MoS₂It is miscellaneous that other are not observed in nano flake The characteristic peak of matter.MoS₂Go out peak position and MoS₂- IL's is essentially identical, but MoS₂The peak intensity of-IL is substantially reduced, this is Since IL is filled into MoS₂In the interlayer of piece, so that caused by material is more unordered.In addition, in MoS₂It is observed in the XRD diagram of-IL/GO To the main diffraction peak (being marked by *) of GO, this is consistent with the result of Raman spectrum.

2. the chemical property of modified electrode

The chemical property of modified electrode is studied by cyclic voltammetry (Cyclic voltammetry, CV).Fig. 3 A is aobvious Show that modified electrode is containing 200 μm of olL^-1Phosphate buffer (Phosphate the buffer saline, PBS, pH of CAP 7) CV curve.Although observing specific redox peaks, MoS on all modified electrodes₂The electricity of-IL/GO/GCE Intensity of flow is significantly greater than MoS₂/ GCE, MoS₂- IL/GCE and GO/GCE.Compared with naked GCE, the introducing of IL improves current-responsive, This may be attributed to stratiform MoS₂The chemical property and MoS of piece modified electrode₂With IL to the synergic catalytic effect of CAP [34].In MoS₂Maximum current intensity is observed on-IL/GO/GCE, it is further that this may be attributed to modified electrode caused by GO Increased surface area and higher conductivity.In forward scan, MoS₂The voltammogram of-IL/GO/GCE in 0.129V and Cathode peak is provided at 0.656V, anode peak is provided at 0.067V in reverse scan.Cathode peak is attributed in CAP nitro not (scheme 2, reaction a) explain that anode peak is attributed to the reversible oxygen that intermediate hydroxyamine groups generate nitroso-derivative to reversible reduction Change reduction reaction [29,30], shown in following reaction formula (reaction b, c).Based on cathode peak (0.656V) higher peak point current, choosing It is selected to develop sensitive CAP sensor.

In addition, as shown in Figure 3B electrochemical impedance spectroscopy (Electrochemical impedance spectroscopy, EIS it) has been represented as nyquist diagram, has been used to check the electrical property of modified electrode.Fe(CN)₆ ^3-/4-As redox probe. Half diameter of a circle corresponds to charge transfer resistance (Charge transfer resistance, R in nyquist diagram_ct), it is different Half diameter of a circle of EIS curve of modified electrode is different.R_ctIntensity sequence is：MoS₂-IL/GO/GCE<GO/GCE<MoS₂-IL/ GCE<MoS₂/GCE<GCE.The result shows that the material of institute of institute modified electrode can reduce electrode R_ct.Wherein, due to synthetic material compared with High conductivity, MoS₂The Rct of-IL/GO/GCE is significantly lower than naked GCE and reference electrode.CV and EIS result shows MoS₂-IL/ GO modified electrode has good chemical property.

3. the optimization of experiment condition

In order to realize the sensitivity detection to CAP, modification amount and the condition of pH are systematically optimized.As shown in Figure 4 A, 3 μ L MoS₂- IL/GO suspension (1.0mg mL^-1) current strength when being added drop-wise to the surface GCE is maximum, as modifier volume is into one Step increases current strength reduces (Fig. 4 B) instead.This is because MoS₂- IL/GO can effectively increase the surface area of electrode, but thicker The superposition of layer may interfere with the conductivity of electrode.Select MoS₂The optimal dose of-IL/GO suspension is 3 μ L.

Fig. 4 C shows the influence of PBS buffer solution pH.CAP peak point current increases as pH increases to 7 from 5, and Reach maximum when pH 7.9 from pH 7 to pH, peak point current is gradually reduced.In addition, being presented between different pH value and spike potential good Good linear relationship (Fig. 4 D), this shows that proton participates in the process [36] of redox reaction.Therefore, selected optimal pH for 7 PBS solution.

In addition, to further determine that MoS₂Reaction mechanism between-IL/GO/GCE and CAP has inquired into sweep speed to oxygen Change the influence (Fig. 5 A) of reduction peak current.It is 20mVs in sweep speed^-1-140mV·s^-1When, redox current is with sweeping It retouches the increase of rate and increases, and linear relationship (Fig. 5 B) is presented between peak current and sweep speed, electrode when this is detection CAP Surface limited is in the characteristic behavior of electro-catalysis process.

4. detecting the CAP of various concentration

The CAP of various concentration is detected by DPV in optimal conditions.As shown in Figure 6 A and 6 B, with the increasing of CAP concentration Add, is also gradually increased in the reduction peak current of 0.604V, and in 0.1-400 μm of olL^-1It is directly proportional to CAP concentration in range. Regression equation is I (μ A)=0.3018C_CAP-1.331(0.1-400μmol·L^-1, R²=0.9941) and I (μ A)= 0.3665C_CAP+0.0379(0.1-10μmol·L^-1, R²=0.9967).The detection of CAP is limited to 0.047 μm of olL^-1(S/N= 3).By the way that compared with the electrochemical sensor for CAP detection reported before (table 1), this sensor sheet reveals quite very To better performance.

Table 1. detects the comparison between the different electrochemical sensors of CAP.

^aRGO (Reduced graphene oxide) is redox graphene, AuNPs (Au nanoparticles) For gold nano grain.

5. stability, repeatability and reproducibility

Modified electrode is used to detect 200 μm of olL after storing at room temperature 10 days^-1CAP, analysis performance still keep initial The 92.94% of electrode shows that sensor is with good stability.By single modified electrode to 200 μm of olL^-1CAP carries out ten Secondary duplicate measurements, the electrode show that excellent repeatability, relative standard deviation (RSD) are 2.605%.In addition, by using 10 modified electrodes measure 200 μm of olL^-1CAP, RSD 2.877% shows that modified electrode has good reproducibility.

6. actual sample is analyzed

By detecting different types of actual sample, such as CAP eye drops, milk and urine assess MoS₂-IL/GO/GCE Detect the application potential of CAP.CAP eye drops, milk and urine use 0.1molL respectively^-1PBS (pH 7) solution dilution 40,5,5 Times, it the results are shown in Table 2.The rate of recovery of actual sample CAP is 90.70%-100.4%.The result shows that MoS₂- IL/GO/GCE application It is analyzed in actual sample, is a kind of promising electrochemical sensor.

Table 2.MoS₂Mark-on reclaims of-the IL/GO/GCE in actual sample.

^aCAP. is not detected in milk and urine

7. conclusion

By simplicity, green and efficient method has successfully synthesized a kind of novel MoS₂- IL/GO composite material.SEM, TEM, Raman spectrum and XRD result confirm MoS₂The synthesis of-IL/GO.MoS2-IL/GO modified GCE shows excellent electricity Chemical property and electro-catalysis ability.At optimum conditions, which may be implemented the high sensitivity measuring to CAP, Detection range is wide, and detection limits low, favorable reproducibility, and stability is good, and shows good electrochemistry when detecting actual sample Energy.

So far, although those skilled in the art will appreciate that present invention has been shown and described in detail herein multiple shows Example property embodiment still without departing from the spirit and scope of the present invention, still can according to the present disclosure directly Determine or deduce out many other variations or modifications consistent with the principles of the invention.Therefore, the scope of the present invention is understood that and recognizes It is set to and covers all such other variations or modifications.

Bibliography of the invention is as follows：

1.Novoselov KS,Geim AK,Morozov SV,Jiang D,Zhang Y,Dubonos SV, Grigorieva IV,Firsov AA(2004)Electric field effect in atomically thin carbon films.Science 306(5696):666-669

2.Kong RM,Ding L,Wang Z,You J,Qu F(2015)Anovel aptamer-functionalized MoS 2nanosheet fluorescent biosensor for sensitive detection of prostate specific antigen.Anal Bioanal Chem 407(2):369-377

3.Radisavljevic B,Radenovic A,Brivio J,Giacometti V,Kis A(2011) Single-layer MoS2transistors.Nat Nanotechnology 6(3):147-150

4.Yuk JM,Park J,Ercius P,Kim K,Hellebusch DJ,Crommie MF,Lee JY,Zettl A,Alivisatos AP(2012)High-resolution EM of colloidal nanocrystal growth using graphene liquid cells.Science 336(6077):61-64

5.Guan G,Zhang S,Liu S,Cai Y,Low M,Teng CP,Phang IY,Cheng Y,Duei KL, Srinivasan BM(2015)Protein Induces Layer-by-Layer Exfoliation of Transition Metal Dichalcogenides.J Am Chem Soc 137(19):6152-6155

6.Kim J,Kim S(2014)Preparation and electrochemical property of ionic liquid-attached graphene nanosheets for an application of supercapacitor electrode.Electrochim Acta 119(6):11-15

7.Abbasi P,Asadi M,Liu C,Sharifi-Asl S,Sayahpour B,Behranginia A, Zapol P,Shahbazian-Yassar R,Curtiss LA,Salehi-Khojin A(2017)Tailoring the Edge Structure of Molybdenum Disulfide toward Electrocatalytic Reduction of Carbon Dioxide.ACS Nano 11(1):453-460

8.Zhang W,Wang Y,Zhang D,Yu S,Zhu W,Wang J,Zheng F,Wang S,Wang J (2015)A one-step approach to the large-scale synthesis of functionalized MoS2 nanosheets by ionic liquid assisted grinding.Nanoscale 7(22):10210-10217

9.Shang NG,Papakonstantinou P,Sharma S,Lubarsky G,Li M,Mcneill DW, Quinn AJ,Zhou W,Blackley R(2012)Controllable selective exfoliation of high- quality graphene nanosheets and nanodots by ionic liquid assisted grinding.Chem Commun 48(13):1877-1879

10.Wang Y,Ou JZ,Balendhran S,Chrimes AF,Mortazavi M,Yao DD,Field MR, Latham K,Bansal V,Friend JR(2013)Electrochemical Control of Photoluminescence in Two-Dimensional MoS2 Nanoflakes.Acs Nano 7(11):10083-10093

11.Asadi M,Kumar B,Liu C,Phillips P,Yasaei P,Behranginia A,Zapol P, Klie RF,Curtiss LA,Salehi-Khojin A(2016)Cathode Based on Molybdenum Disulfide Nanoflakes for Lithium-Oxygen Batteries.ACS Nano 10(2):2167-2175

12.Lau VW,Masters AF,Bond AM,Maschmeyer T(2012)Ionic-liquid-mediated active-site control of MoS2 for the electrocatalytic hydrogen evolution reaction.Chem-Eur J 18(26):8230-8239

13.Wang GX,Bao WJ,Wang J,Lu QQ,Xia XH(2013)Immobilization and catalytic activity of horseradish peroxidase on molybdenum disulfide nanosheets modified electrode.Electrochem Commun 35(10):146-148

14.Chekin F,Teodorescu F,Coffinier Y,Pan GH,Barras A,Boukherroub R, Szunerits S(2016)MoS2/reduced graphene oxide as active hybrid material for the electrochemical detection of folic acid in human serum.Biosens Bioelectron 85:807-813

15.Armenta S,Guardia MDL,Abad-Fuentes A,Abad-Somovilla A,Esteve- Turrillas FA(2016)Highly selective solid-phase extraction sorbents for chloramphenicol determination in food and urine by ion mobility spectrometry.Anal Bioanal Chem 408(29):1-9

16.Kong FY,Chen TT,Wang JY,Fang HL,Fan DH,Wang W(2016)UV-assisted synthesis of tetrapods-like titanium nitride-reduced graphene oxide nanohybrids for electrochemical determination of chloramphenicol.Sensors& Actuators B Chemical 225:298-304

17.Codognoto L,Winter E,Doretto KM,Monteiro GB,Rath S(2010) Electroanalytical performance of self-assembled monolayer gold electrode for chloramphenicol determination.Microchim Acta 169(3-4):345-351

18.Wiest DB,Cochran JB,Tecklenburg FW(2012)Chloramphenicol toxicity revisited:a 12-year-old patient with a brain abscess.Journal of Pediatric Pharmacology&Therapeutics Jppt the Official Journal of Ppag 17(2):182-188

19.Duan N,Wu S,Dai S,Gu H,Hao L,Ye H,Wang Z(2016)Advances in aptasensors for the detection of food contaminants.Analyst 141(13):3942-3961

20.Bagheri Hashkavayi A,Bakhsh Raoof J,Ojani R,Hamidi Asl E(2015) Label-Free Electrochemical Aptasensor for Determination of Chloramphenicol Based on Gold Nanocubes-Modified Screen-Printed Gold Electrode.Electroanal 27 (6):1449-1456

21.Satínsky D,Chocholous P,SalabováM,Solich P(2015)Simple determination of betamethasone and chloramphenicol in a pharmaceutical preparation using a short monolithic column coupled to a sequential injection system.J Sep Sci 29(16):2494-2499

22.Yadav SK,Agrawal B,Chandra P,Goyal RN(2014)In vitro chloramphenicol detection in a Haemophilus influenza model using an aptamer- polymer based electrochemical biosensor.Biosens Bioelectron 55(4):337-342

23.Yan Z,Gan N,Wang D,Cao Y,Chen M,Li T,Chen Y(2015)A"signal-on” aptasensor for simultaneous detection of chloramphenicol and polychlorinated biphenyls using multi-metal ions encoded nanospherical brushes as tracers.Biosens Bioelectron 74(49):718-724

24.Govindasamy M,Chen SM,Mani V,Devasenathipathy R,Umamaheswari R, Joseph Santhanaraj K,Sathiyan A(2017)Molybdenum disulfide nanosheets coated multiwalled carbon nanotubes composite for highly sensitive determination of chloramphenicol in food samples milk,honey and powdered milk.J colloid interf sci 485:129-136

25.Abnous K,Danesh NM,Ramezani M,Emrani AS,Taghdisi SM(2016)A novel colorimetric sandwich aptasensor based on an indirect competitive enzyme-free method for ultrasensitive detection of chloramphenicol.Biosens Bioelectron 78:80-86

26.Karthik R,Govindasamy M,Chen SM,Mani V,Lou BS,Devasenathipathy R, Hou YS,Elangovan A(2016)Green synthesized gold nanoparticles decorated graphene oxide for sensitive determination of chloramphenicol in milk, powdered milk,honey and eye drops.J colloid interf sci 475:46-56

27.Tai SY,Liu CJ,Chou SW,Chien SS,Lin JY,Lin TW(2012)Few-layer MoS2 nanosheets coated onto multi-walled carbon nanotubes as a low-cost and highly electrocatalytic counter electrode for dye-sensitized solar cells.J Mater Chem 22(47):24753-24759

28.Asadi M,Kumar B,Liu C,Phillips P,Yasaei P,Behranginia A,Zapol P, Klie RF,Curtiss LA,Salehikhojin A(2016)Cathode Based on Molybdenum Disulfide Nanoflakes for Lithium–Oxygen Batteries.Acs Nano 10(2):2167

29.Yang G,Zhao F(2015)Electrochemical sensor for chloramphenicol based on novel multiwalled carbon nanotubes@molecularly imprinted polymer.Biosens Bioelectron 64:416-422

30.Fedorczyk A,Ratajczak J,Kuzmych O,Skompska M(2015)Kinetic studies of catalytic reduction of 4-nitrophenol with NaBH 4 by means of Au nanoparticles dispersed in a conducting polymer matrix.J Solid State Electrochem 19(9):2849-2858

31.Zhang X,Zhang YC,Zhang JW(2016)A highly selective electrochemical sensor for chloramphenicol based on three-dimensional reduced graphene oxide architectures.Talanta 161:567

32.Tao Y,Huaiyin C,Tong G,Jin W,Weihua L,Kui J(2015)Highly sensitive determination of chloramphenicol based on thin-layered MoS2/polyaniline nanocomposite.Talanta 144:1324-1328

33.Borowiec J,Wang R,Zhu L,Zhang J(2013)Synthesis of nitrogen-doped graphene nanosheets decorated with gold nanoparticles as an improved sensor for electrochemical determination of chloramphenicol.Electrochim Acta 99:138- 144。

Claims (10)

1. a kind of composite material of molybdenum disulfide and graphene oxide based on ionic liquid, it is characterised in that：The composite wood Material has formula MoS₂-IL/GO。

2. the composite material of the molybdenum disulfide and graphene oxide according to claim 1 based on ionic liquid, feature It is：The IL is 1- butyl -3- methyl imidazolium tetrafluoroborate [BMIM] BF₄。

3. a kind of composite material for preparing the molybdenum disulfide based on ionic liquid and graphene oxide of any of claims 1 or 2 Method, which is characterized in that described method includes following steps：

(1) by MoS₂It is moved in DMF with IL, ultrasound 15 hours；

(2) step (1) is added into GO obtains MoS₂-IL(1g·L^-1), and mixture is 30 minutes ultrasonic again at room temperature；

(3) it is centrifuged, black object is washed with water and is dispersed again in DMF, obtain MoS₂- IL/GO nanocomposite.

4. according to the method described in claim 3, it is characterized in that：The IL is 1- butyl -3- methyl imidazolium tetrafluoroborate [BMIM]BF₄。

5. a kind of modified electrode, it is characterised in that：The modified electrode is with of any of claims 1 or 2 based on ionic liquid The composite material of molybdenum disulfide and graphene oxide is modified.

6. modified electrode according to claim 6, it is characterised in that：The modified electrode is modified glass-carbon electrode.

7. a kind of electrochemical sensor, it is characterised in that：The electrochemical sensor includes glass carbon described in claim 5 or 6 Electrode.

8. application of the electrochemical sensor according to claim 7 in detection chloramphenicol.

9. application according to claim 8, it is characterised in that：The detection of the detection is limited to 0.047 μm of olL^-1。

10. application according to claim 8, it is characterised in that：The application is for eye drops, milk and urine sample The measurement of middle chloramphenicol.