阅读说明：本技术 一种检测水体中酚类化合物的传感器件及其制备方法 (The senser element and preparation method thereof of phenolic compound in a kind of detection water body ) 是由 刘建允 朱国栋 唐倩 窦金磊 李旋 胡彬 史威 聂鹏飞 杨洪梅 于 2019-09-03 设计创作，主要内容包括：本发明涉及一种检测水体中酚类化合物的传感器件及其制备方法,将聚苯胺纳米管和氧化石墨烯通过简单的混合搅拌,再离心提取得到了石墨烯和聚苯胺纳米管复合材料。本发明采用的修饰电极制作方法简单,绿色环保,用该修饰电极组装的传感器件可用于水体中酚类化合物的同时检测。由于制备的石墨烯包覆在聚苯胺纳米管的表面且聚苯胺纳米管分布均匀,用该材料修饰电极并组装电化学传感器,用于酚类化合物的检测,具有较高的选择性和灵敏度。(The present invention relates to a kind of senser elements and preparation method thereof of phenolic compound in detection water body, and polyaniline nanotube and graphene oxide are passed through and are simply mixed, then is centrifuged extraction and has obtained graphene and polyaniline nanotube composite material.The modified electrode production method that the present invention uses is simple, environmentally protective, detection while can be used for phenolic compound in water body with the senser element that the modified electrode assembles.Due to preparation graphene coated polyaniline nanotube surface and polyaniline nanotube be evenly distributed, with the material modified electrode and assemble electrochemical sensor, for the detection of phenolic compound, selectivity with higher and sensitivity.)

1. a kind of graphene/polyaniline nanometer tube composite materials, which is characterized in that the composite material is graphene coated poly- Aniline nano pipe surface；Wherein polyaniline nanotube is nano tubular structure, and wherein the internal diameter of pipe is 50-1000nm, and outer diameter is 200-1500nm, nanotube length are 0.1-20 μm.

2. composite material according to claim 1, which is characterized in that the bore of the polyaniline nanotube is 100- 500nm, outer diameter 300-800nm, nanotube length are 0.5-10 μm.

3. a kind of preparation method of graphene/polyaniline nanometer tube composite materials, comprising:

Polyaniline nanotube dispersion liquid, graphene oxide dispersion are mixed, 12h is stirred, is centrifuged, is washed, vacuum drying obtains Graphene/polyaniline nanotube.

4. preparation method according to claim 3, which is characterized in that the solvent of the polyaniline nanotube dispersion liquid is anhydrous Ethyl alcohol；The solvent of graphene oxide dispersion is water.

5. preparation method according to claim 3, which is characterized in that the concentration of the polyaniline nanotube dispersion liquid is 0.05-5.0g/L；The concentration of graphene oxide dispersion is 0.05-5.0g/L；The quality of polyaniline nanotube, graphene oxide Than for 1:2~1:7.

6. a kind of electrochemical sensing device based on graphene/polyaniline nanometer tube composite materials described in claim 1.

7. electrochemical sensing device according to claim 6, which is characterized in that by graphene/polyaniline described in claim 1 Nanotube PANI-GO Yu Shuizhong ultrasonic disperse, then drop coating to conductive substrates, obtains working electrode；Then by working electrode, ginseng Than electrode, electrode is inserted into electrolyte solution, and is connected with electrochemical workstation and constitutes circuit, electrochemical workstation and computer It is connected, assembling obtains electrochemical sensing device.

8. electrochemical sensing device according to claim 7, which is characterized in that the reference electrode is Ag/AgCl reference, satisfies And calomel electrode, one of standard hydrogen electrode；It is inactive, conductive material to electrode；Electrolyte solution is containing phenolic compound Supporting electrolyte solution；Wherein the supporting electrolyte solution is phosphate buffer Na₂HPO₄-NaH₂PO₄, sodium acetate buffer One or more of liquid HAc-NaAc, Bloomsbury be smooth-Robison's buffer solution Britton-Robinson solution；Supporting electrolyte The concentration of solution is 0.05~2.0mol/L, and pH range is 2~9.

9. electrochemical sensing device according to claim 8, which is characterized in that the phenolic compound is phenol, to nitro Phenol, bisphenol-A, 2- cresols, 4- chlorophenol, one or more of p-cresol.

10. electrochemical sensing device described in a kind of claim 6 measures one or more of phenolic compounds in water body at the same time Using.

Technical field

The invention belongs to phenolic compounds to test device and preparation method thereof field, in particular to phenol in a kind of detection water body The senser element and preparation method thereof of class compound.

Background technique

Phenolic compound prepares drug, paper, insecticide, the polymeric material of resinae as a kind of important raw material of industry In material and plastic products.And phenols can be moved in organism by food chain or drinking water by external environment, cause to give birth to Grow obstacle, cancer is immunized and the problems such as nervous system.Phenols is classified as preferential toxic contaminants by many national organizations Object inventory, including Environmental Protection Agency USA, [F.R.Edstac, the Endocrine Disrupter such as European Food Safety Authority Screening and Testing Advisory Committee(EDSTAC)report,1998]." Drinking Water health Standard " in regulation, volatile phenol contents be no more than 0.002mg/L." food containers and packaging material polycarbonate resin health Standard ", the inside provides bisphenol-A dosage: being exactly phenol palpus≤0.05mg contained in one liter of distilled water (i.e.≤0.05ppm)；This Require more highly sensitive detector.Currently, having to the method for phenolic compound detection: gas chromatography-mass spectrometry, efficiently Liquid chromatogram, molecular engram, fluorescence and enzyme linked immunosorbent assay etc..These methods are sensitive and reliable, but expensive instrument at This, the pretreatment of time-consuming operating procedure and complexity limits the application of their on-site tests.In comparison, Electrochemical Detection by It is easy to operate in low cost, different selectivity of fine quality to detectable substance and high sensitivity and the extensive concern for causing people.But It is the damage due to lower sensitivity and phenols oxidation product to bare electrode, highly sensitive inspection of the bare electrode to phenolic compound Survey is unworkable.Therefore, exploitation to the electrochemical sensor of the highly sensitive detection of phenolic compound be researchers urgently Problem [Analytica Chimica Acta, 853 (2015) 249-257] to be solved.Particularly, bis-phenol in phenolic comp ' ds pollution A and the phenol oxidizing potential on bare electrode are closer to, and peak difference in peak is smaller, can influence each other, and can not be detected simultaneously.Therefore, it opens It is very necessary to issue senser element that is a kind of while detecting bisphenol-A and phenol.

A kind of conductive polymer polymer of the polyaniline as classics, is easy to get with raw material, and synthesis is simple, protonic acid doping And excellent chemical property, it is widely used in and prepares electrode material and biology or electrochemical sensor etc..But traditional chemistry The polyaniline of polymerization is easy to reunite, and active site is not exposed sufficiently, electron transport ability and the detectability to analyte It is poor.Compared to traditional polyaniline, the polyaniline nanotube of tubulose specific surface area with higher and excellent electron-transport Ability [ACS Nano, 5 (2011) 3469-3474], by effective compound with graphene oxide, graphene coated is in polyaniline Nanotube surface, the two form synergistic effect, and electric conductivity and chemical property further promote, enhance the absorption of analyte with Accumulation ability is greatly improved the detection sensitivity to analyte.

Simultaneously as the excellent electron transport ability and high specific surface area of polyaniline nanotube, equal using graphene Even cladding polyaniline nanotube prepares electrochemical sensor, is greatly improved phenolic compound in the sensitive sound of the sensor surface It answers.

106024427 A of CN discloses ultra-thin graphene membrane electrode and its preparation of a kind of modification of polyaniline nanotube Method is first compounded to form graphene/manganese dioxide nano fiber laminated film by graphene and manganese dioxide, with manganese dioxide fibre Tieing up film is that matrix polymerization forms polyaniline nanotube, to obtain the graphene composite film of polyaniline nanotube modification, is made Standby application of electrode is in supercapacitor.The preparation of electrode is needed using manganese dioxide nano fiber as template in the patent, dioxy It is not easy to control to change uniformity of the manganese nanofiber on graphene, sees in apparent from the scanning electron microscope (SEM) photograph difficulty or ease for preparing electrode Blank pipe shape polyaniline fiber, polyaniline nano fiber is shorter and overall distribution is uneven.And preparation method of the present invention is simple, is not required to Want manganese dioxide fiber etc. as template, the controlled diameter of polyaniline nanotube, polyaniline nano length of tube is longer and preparation Graphene coated polyaniline nanotube is integrally uniformly dispersed, and can be used for phenol generalization in water body with electrochemical sensing device is prepared Close the detection of object.

Summary of the invention

Technical problem to be solved by the invention is to provide it is a kind of detection water body in phenolic compound senser element and its Preparation method overcomes that phenols (such as bisphenol-A, phenol) oxidizing potential on bare electrode is relatively close and the defect that cannot detect simultaneously, Using the electrochemical sensor of graphene coated polyaniline nanotube modified electrode assembling for phenol generalization in water body in the present invention Close the highly sensitive detection of object (such as bisphenol-A, phenol).

A kind of graphene/polyaniline nanometer tube composite materials of the invention, the composite material are graphene coated poly- Aniline nano pipe surface；Wherein polyaniline nanotube is nano tubular structure, and wherein the internal diameter of pipe is 50-1000nm, and outer diameter is 200-1500nm, nanotube length are 0.1-20 μm.

Further, the bore of the preferably described polyaniline nanotube is 100-500nm, outer diameter 300-800nm, nanotube Length is 0.5-10 μm.

A kind of preparation method of graphene/polyaniline nanometer tube composite materials of the invention, comprising:

Polyaniline nanotube dispersion liquid, graphene oxide dispersion are mixed, 12h is stirred, is centrifuged, is washed, vacuum drying Obtain graphene/polyaniline nanotube.

The preferred embodiment of above-mentioned preparation method is as follows:

The solvent of the polyaniline nanotube dispersion liquid is dehydrated alcohol；The solvent of graphene oxide dispersion is water.

The polyaniline nanotube dispersion liquid, graphene oxide dispersion specifically: by graphene oxide in ultrapure water, Ultrasonic disperse is uniform；Take a certain amount of polyaniline nanotube in ethanol solution, ultrasonic disperse is uniform；Wherein ultrasonic time It is 0.2-3h, preferably 1-2h.

The concentration of the polyaniline nanotube dispersion liquid is 0.05-5.0g/L；The concentration of graphene oxide dispersion is 0.05-5.0g/L；Preferred concentration is preferred 0.1-0.3g/L.

The polyaniline nanotube, graphene oxide mass ratio be 1:2~1:7, preferably 1:5.

The centrifugal rotational speed is 8000-11000rpm, preferably 10000rpm.

The present invention provides a kind of electrochemical sensing device based on the graphene/polyaniline nanometer tube composite materials.

Further, by the graphene/polyaniline nanotube PANI-GO Yu Shuizhong ultrasonic disperse, dispersion liquid is obtained, then Drop coating obtains working electrode to conductive substrates；Then by working electrode, reference electrode is inserted into electrolyte solution electrode, and It is connected with electrochemical workstation and constitutes circuit, electrochemical workstation is connected with computer, and assembling obtains electrochemical sensing device.

The graphene/polyaniline nanotube PANI-GO Yu Shuizhong ultrasonic disperse, wherein dispersion liquid concentration is 0.05- 3.0g/L, preferably 0.2g/L, ultrasonic time 0.5-3h, preferably 2h.

The conductive substrates are glass-carbon electrode, gold electrode, one kind of graphite electrode, silver electrode etc.；Reference electrode is Ag/ AgCl reference, saturated calomel electrode, one of standard hydrogen electrode；It is inactive, conductive material (such as Pt, Pt piece) to electrode；Electricity Electrolyte solution is the supporting electrolyte solution containing phenolic compound；Wherein the supporting electrolyte solution is phosphate buffer (Na₂HPO₄-NaH₂PO₄), sodium-acetate buffer (HAc-NaAc), Bloomsbury it is smooth-Robison's buffer solution (Britton- Robinson) one or more of solution；The concentration of supporting electrolyte solution is 0.05~2.0mol/L, preferably 0.1mol/ L；PH range is 2~9, preferably pH=7.0.

The phenolic compound is phenol, paranitrophenol, bisphenol-A, 2- cresols, 4- chlorophenol, one of p-cresol Or it is several；Preferably, the one or two of bisphenol-A, phenol.

Include electrochemical workstation in electrochemical sensing device of the invention, controls software and data collection system；Work Electrode, reference electrode and it is connected to electrode with electrochemical workstation, is inserted into the electrolyte solution of bisphenol-A and phenol and constitutes back Road；Electrochemical workstation is connected with computer, records electric current under different potentials under selected test method by control software Variation.

The electrochemical sensing device needs to test a series of titer of the phenolic compound of known concentrations, by phenols The concentration and size of current of compound draw standard curve；Again by test unknown concentration phenolic compound solution, phenol is calculated The concentration of class compound

The present invention provides a kind of electrochemical sensing device and measures one or more of phenolic compounds in water body at the same time Application.Further, a kind of electrochemical sensing device measures the application of bisphenol-A and/or phenol in water body at the same time.

Beneficial effect

(1) present invention using polyaniline itself redox characteristic and polyaniline and graphene between Electrostatic Absorption and Polyaniline nanotube and graphene oxide are passed through and are simply mixed, then be centrifuged extraction and obtain by the interaction of pi-pi bond Graphene and polyaniline nanotube composite material, preparation method is simple by the present invention, without the addition of high temperature and reducing agent, ring Protect pollution-free, polyaniline nanotube is evenly distributed on graphene sheet layer and by graphene coated, prepares dispersion liquid drop coating and repairs Electrode is adornd, the polyaniline nanotube modified electrode of graphene coated can be obtained；

(2) present invention is prepared for graphene coated polyaniline nanotube modified electrode, utilizes polyaniline and graphene oxide Between redox reaction after obtain, method is simple, good dispersion, the addition without reducing agent；

(3) present invention utilizes the high specific surface area of tubulose polyaniline nanotube and excellent electron transfer rate, graphite Alkene is uniformly coated on the surface of polyaniline nanotube, uniformly compound by the two, and active site becomes more, the transmission speed of electronics Rate becomes faster, sensitiveer to the detection of phenols (Fig. 4, Fig. 5), and electro-chemical activity enhancing is conducive to detection of the sensor to pollutant；

(4) graphene coated polyaniline nanotube modified electrode prepared by the present invention, is assembled into electrochemical sensor, modification On electrode the oxidizing potential peak peak of bisphenol-A and phenol difference it is larger, it can be achieved that while bisphenol-A and phenol detection do not interfere with each other； And since the oxidizing potential peak peak difference of bisphenol-A and phenol is smaller on bare electrode, it cannot detect simultaneously；

(5) electrode modified material polyaniline nanotube in the present invention has high ratio compared to traditional polyaniline material Surface area and excellent electrode transmittability, polyaniline nanotube are coated by graphene uniform, and be evenly distributed soilless sticking, enhances The electric conductivity and chemical property of material, thus the phenolic compound in electrochemical sensor measurement water is prepared as electrode material (such as bisphenol-A, phenol) has high sensitivity；

(6) a kind of senser element for measuring phenolic compound in water body simultaneously prepared by the present invention, for bisphenol-A in water body With Electrochemical Detection while phenol, there is lower detection limit (nM) and the wider range of linearity (Fig. 4, Fig. 5).

Detailed description of the invention

Fig. 1 is surface sweeping Electronic Speculum (SEM) figure of the polyaniline nanotube in the embodiment of the present invention 2；

Fig. 2 be in the embodiment of the present invention 2 polyaniline nanotube in HAc-NaAc (pH=4.6) cyclic voltammogram；

Fig. 3 is the polyaniline nanotube (A) being dispersed on glass-carbon electrode in the embodiment of the present invention 2, and graphene coated is poly- The SEM of aniline nano pipe (B) schemes；

Fig. 4 is the electrochemical sensor of the PANI-GO modified electrode preparation in the embodiment of the present invention 2 to various concentration bis-phenol The linear calibration curve figure (B) of the differential pulse voltammetry figure (A) of A and corresponding concentration and oxidation peak current；

Fig. 5 is the electrochemical sensor of in the embodiment of the present invention 2 PANI-GO modified electrode preparation to various concentration phenol Differential pulse voltammetry figure (A) and corresponding concentration and oxidation peak current linear calibration curve figure (B)；

Fig. 6 is measurement of the bare electrode (bare) to bisphenol-A (A) and phenol (B) in the embodiment of the present invention 3；

Fig. 7 is measurement of the PANI-GO modified electrode (A, B) to bisphenol-A and phenol in the embodiment of the present invention 2；

Fig. 8 is differentiated pulse voltammogram (A) of the PANI-GO modified electrode in the embodiment of the present invention 2 to bisphenol-A and phenol With the linearity correction figure (B) of concentration and electric current；

Fig. 9 is one of embodiment of the present invention while the senser element schematic diagram for measuring phenolic compound in water body: 1. Control software and data processing system；2. electrochemical workstation；3. working electrode；4. reference electrode；5. pair electrode；6. buffering molten Liquid.

Specific embodiment

Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.