CN103980424A - Graphene-poly ionic liquid composite material, and preparation method and application thereof - Google Patents
Graphene-poly ionic liquid composite material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene-poly ionic liquid composite material, and a preparation method and application thereof. The preparation method comprises the following steps: under the protection of inert gas, conducting a free radical polymerization reaction on the graphene and an ionic liquid with ethylenic bond in the presence of an initiator; and after the reaction, washing and drying the reaction products to obtain the graphene-poly ionic liquid composite material. As the graphene-poly ionic liquid composite material has good conductivity, porous structure and high adsorption, it can be used to prepare an electrochemical sensor for detection of phenylethanolamine A. The preparation method of the invention has the advantages of simple operation, low cost and easy control of the reaction process; the obtained graphene-poly ionic liquid composite material has the advantages of high sensitivity, high stability and recyclability; and the electrochemical sensor can fast and accurately detect phenylethanolamine A.
Description
Technical field
The invention belongs to electrochemical sensor technical field, be specifically related to a kind of Graphene-poly ion liquid matrix material and its preparation method and application.
Background technology
Phenylethanolamine A (PEA) is the by product of Ractopamine hydrochloride in building-up process, is the isomers of formoterol.It is the same with Clenbuterol hydrochloride and Ractopamine hydrochloride, has nutrition reallocation effect, is a kind of beta-receptor agonist.But it is the growth stimulant as domestic animal by misuse also, makes fat in animal body become lean meat, thereby is considered to a kind of novel clenbuterol hydrochloride.2010, the multiple provinces of China detected PEA in pig urine, and PEA residual in pork can cause severe side effect, such as there will be the symptoms such as nauseating, dizziness, myasthenia of the limbs, hand tremor, particularly to there being heart trouble and hyperpietic's harm larger.The long-term edible food that contains this material can cause chromosome aberration and cause malignant tumour, serious harm people's health.Therefore setting up quick, easy, sensitive Phenylethanolamine A detection method is necessary.
Electrochemical sensor is that a kind of simple to operate, high sensibility, highly selective, analysis are quick, inexpensive, durable, the direct extremely low analytical equipment of working sample content, at present electrochemical sensor develop into one of the most active field in boundary of analyzing.The key of electrochemical sensor is to prepare chemically modified electrode, chemically modified electrode is that people receive electrode surface specific chemical group, builds surface micro-structure, gives electrode certain specific performance, as selectivity, pre-concentration processing to analysis component, electrocatalytic reaction speed etc.
Graphene is by having sp
2the flat film of the hexagonal honeycomb lattice structure of the carbon atom composition of hybridized orbital is a kind of two-dimensional material of only having a carbon atom thickness.It has the features such as good electrical property, mechanical property and thermostability, therefore utilizes Graphene for raw material synthesis of nano mixture, and using this nano-complex as electrode modified material, can build electrochemical sensor of new generation.
The Chinese patent literature that is CN103387564A as notification number discloses a kind of carboxylated graphene oxide-ionic liquid composite nano materials, its preparation method comprises: (1) is by graphene oxide, solid sodium hydroxide and Mono Chloro Acetic Acid are water-soluble, graphene oxide, solid sodium hydroxide, Mono Chloro Acetic Acid three's mass ratio is (5-20): (400-600): (400-600), ultrasonic even, stirring reaction 2 hours, centrifugation, solid washes with water to neutrality, vacuum-drying at 60 DEG C, obtain carboxylated graphene oxide, carboxylated gained graphene oxide is joined in 0.01mol/L NaOH solution, solid-to-liquid ratio is 0.8-1.2mg:1mL, stir 2h, centrifugal, solid washes with water to neutrality, vacuum-drying at 60 DEG C, obtain the carboxylated graphene oxide of the form of alkalizing, (2) carboxylated graphene oxide and ionic liquid 4-hydroxyl-1-methyl isophthalic acid-(3-pyrroles's propyl group)-piperidines bromine salt of alkalization form are added in water with the mass ratio of 9:150-250, stirring reaction 1h at 40 DEG C, centrifugation, solid washes with water, then vacuum-drying at 60 DEG C, to obtain final product.This carboxylated graphene oxide-ionic liquid composite nano materials is coated to glass-carbon electrode surface, obtains a kind of electrochemical sensor for detection of Honokiol.
The weak point of this carboxylated graphene oxide-ionic liquid composite nano materials is, in matrix material, compound between ionic liquid and Graphene is only non covalent bond effect, have that ionic liquid comes off, unsettled shortcoming, composite property is unstable, affects the detection sensitivity of electrochemical sensor.
Summary of the invention
The invention provides a kind of Graphene-poly ion liquid matrix material, utilize this matrix material to prepare electrochemical sensor, can be used for detecting quickly and accurately the Phenylethanolamine A in actual sample.
The present invention also provides a kind of preparation method of Graphene-poly ion liquid matrix material, comprising:
Under protection of inert gas, Graphene and ionic liquid with ethylene linkage are carried out to Raolical polymerizable under initiator exists, after react through washing, the described Graphene-poly ion liquid matrix material of dry acquisition.
Graphene-poly ion liquid matrix material of the present invention combines the advantage of Graphene and poly ion liquid, Graphene has good electroconductibility and larger specific surface area, therefore Graphene-poly ion liquid matrix material of the present invention can effectively be improved to electron transfer speed for modified electrode.Poly ion liquid not only has the good electroconductibility of ionic liquid, there is the character that ionic liquid does not possess simultaneously, as vesicular structure, thermo-sensitivity, controlled architecture, both matrix materials have the character of good conductivity, vesicular structure, thermo-sensitivity, vesicular structure is conducive to adsorb Phenylethanolamine A, can improve detection sensitivity.In the matrix material of Graphene-poly ion liquid, poly ion liquid is firmly bonded to Graphene surface by covalent linkage, has good stability simultaneously.
As preferably, described rare gas element is nitrogen, argon gas or helium; More preferably nitrogen.Under protection of inert gas, react, can fully avoid airborne oxygen to impact reaction.
As preferably, the described ionic liquid with ethylene linkage is 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate, 1-allyl group-3-ethyl imidazol(e) phosphofluoric acid hydrochloride or 1-allyl group-3-Methylimidazole villaumite.Can there is radical polymerization in the ionic liquid with ethylene linkage.More preferably 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate, the mass ratio of Graphene and 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate is preferably 1:2～20, more preferably 1:5.
As preferably, described initiator be Diisopropyl azodicarboxylate, Potassium Persulphate or or ammonium sulfate; More preferably Diisopropyl azodicarboxylate.As a kind of azo-initiator, Diisopropyl azodicarboxylate stable reaction, reaction process is easy to control, and can not generate by product.
In the time selecting Diisopropyl azodicarboxylate (AIBN) as initiator, the mass ratio of Graphene, 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate, Diisopropyl azodicarboxylate is preferably: 1:(2～20): (1～6), more preferably 1:5:2.5.More Diisopropyl azodicarboxylate can ensure that Raolical polymerizable carries out completely.
As preferably, the reaction solvent of described Raolical polymerizable can be selected methyl alcohol, ethanol or chloroform.Following principle is followed in choosing of reaction solvent: solvent can not participate in reaction, solvent and can disperse the boiling point of reactant, solvent can reach the needed temperature of reaction, can solvent be removed, is convenient to by simple method the dissolving of initiator after having reacted.
The condition optimization of described Raolical polymerizable is: 60～80 DEG C of temperature of reaction, reaction times 6～18h; More preferably: 70 DEG C of temperature of reaction, reaction times 12h.Temperature of reaction is to be determined by the decomposition temperature of initiator Diisopropyl azodicarboxylate, and its decomposition temperature is 64 DEG C, has therefore selected 70 DEG C.In the time selecting other initiators, temperature of reaction can be adjusted as one sees fit.
Particularly, get 0.02g Graphene and be scattered in 20mL methyl alcohol, after the ultrasonic 30min of 53KHz, add 0.1g1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate, 50mg Diisopropyl azodicarboxylate, more ultrasonic 30min; After inflated with nitrogen 20min, seal flask mouth, in the oil bath of 70 DEG C, react 12h; Reacted rear with ethanol and ultrapure water washing several, vacuum-drying at 70 DEG C, obtains Graphene-poly ion liquid matrix material of the present invention (GR-PIL).
The present invention also provides a kind of electrochemical sensor, comprises working electrode, and the surface of described working electrode is coated with described Graphene-poly ion liquid matrix material.
As preferably, electrochemical sensor of the present invention is three-electrode electro Chemical sensor, working electrode can select surface to be coated with the glass-carbon electrode of described Graphene-poly ion liquid matrix material, and reference electrode can be selected Ag/AgCl electrode, can select platinum electrode to electrode.
In the present invention, the preparation method of described electrochemical sensor is:
(a) by glass-carbon electrode Al
2o
3powder is outstanding sticks with paste polishing, then uses successively dehydrated alcohol and ultrapure water ultrasonic cleaning, and the frequency of each ultrasonic cleaning is 53KHz, and the time is 5-10min; Ultrasonic cleaning completes to be placed in air dries, stand-by;
(b) described Graphene-poly ion liquid matrix material is scattered in DMF, both blending ratios are 5mg:1mL; After ultrasonic mixing, get appropriate mixing solutions and drip and be applied to glass-carbon electrode surface, after drying, obtain GR-PIL modified electrode,
(c) utilizing described GR-PIL modified electrode is working electrode, chooses suitable reference electrode and electrode assembling is become to electrochemical sensor of the present invention.
The present invention also provides described electrochemical sensor in the application detecting in Phenylethanolamine A.When use, the working electrode of described electrochemical sensor is inserted to (liquid to be measured is to obtain in the phosphoric acid buffer by testing sample being dissolved in to pH5.0) in liquid to be measured, after whip attachment 1-8min, take out working electrode, in this liquid to be measured, logical nitrogen to be to remove oxygen, and then working electrode is placed in to this liquid to be measured and carries out the Electrochemical Detection of CV, DPV.
The matrix material of Graphene-poly ion liquid matrix material has the character of good conductivity, vesicular structure, thermo-sensitivity, because poly ion liquid is rich in nitrogen-containing functional group, these functional groups can be with Phenylethanolamine A with hydrogen bonded, so this matrix material can adsorb Phenylethanolamine A in a large number, and strong adsorptivity is conducive to GR-PIL modified electrode raising detection sensitivity.By washing with alcohol or with electrochemical method can be by Phenylethanolamine A wash-out on modified electrode, so just can recycle modified electrode.
Electrochemical sensor of the present invention has high sensitivity to Phenylethanolamine A, and the beta-receptor agonist such as the Clenbuterol hydrochloride that exists in testing sample, Ractopamine hydrochloride, salbutamol all can not disturb the accurate detection of electrochemical sensor of the present invention to Phenylethanolamine A.Electrochemical sensor of the present invention reaches 2.0 × 10 to the detectability of Phenylethanolamine A
-9mol/L.
Compared with prior art, beneficial effect of the present invention is:
Preparation method of the present invention is simple to operate, with low cost, reaction process is easy to control, Graphene-poly ion liquid the matrix material obtaining has high sensitivity, high stability and the feature such as can be recycled, and can detect fast and accurately Phenylethanolamine A.
Brief description of the drawings
Fig. 1 a is the scanning electron microscope analysis result figure of graphene oxide;
Fig. 1 b is the scanning electron microscope analysis result figure of Graphene;
Fig. 1 c is the scanning electron microscope analysis result figure of Graphene-poly ion liquid matrix material;
Fig. 2 is the results of IR figure of graphene oxide, Graphene and Graphene-poly ion liquid matrix material;
Fig. 3 is the X-ray diffraction analytical results figure of graphene oxide, Graphene and Graphene-poly ion liquid matrix material;
Fig. 4 is the thermogravimetric analysis result figure of graphene oxide, Graphene and Graphene-poly ion liquid matrix material;
In Fig. 2,3,4, curve a is graphene oxide, and curve b is Graphene, and curve c is Graphene-poly ion liquid matrix material;
Fig. 5 is that GR-PIL modified electrode is containing 1.0 × 10
-5in the PBS solution of M PEA with PBS blank solution in CV figure; Supporting electrolyte: 0.05M PBS (pH5.0,0.5M NaCl); Adsorption time: 5min; Scanning speed: 100mV/s; Wherein, curve a is PBS blank solution, and curve b is for containing 10 × 10
-5the PBS solution (first lap scanning) of M PEA, curve c is for containing 10 × 10
-5the PBS solution (the second circle scanning) of M PEA;
Fig. 6 is that GCE, PIL/GCE and tri-kinds of electrodes of GR-PIL/GCE are 1.0 × 10
-5dPV response current figure in M PEA solution; Wherein, curve c is GCE electrode, and curve b is PIL/GCE electrode, and curve a is GR-PIL/GCE electrode; Supporting electrolyte: 0.05M PBS (pH5.0,0.5MNaCl) adsorption time: 5min;
Fig. 7 is that GR-PIL/GCE electrode pair PEA response current is with GR-PIL concentration curve;
Fig. 8 is that GR-PIL/GCE electrode pair PEA response current is with adsorption time change curve;
Fig. 9 is that GR-PIL/GCE electrode PEA response current is with ionogen pH change curve;
Figure 10 is that the response current potential of GR-PIL/GCE electrode is with ionogen pH change curve;
Figure 11 a is the linear DPV response curve of GR-PIL/GCE electrode pair different concns PEA; Wherein, curve d-i represents that respectively the concentration (M) of PEA is: 5.0 × 10-
7, 1.0 × 10
-6, 3.0 × 10
-6, 5.0 × 10
-6, 7.0 × 10
-6, 1.0 × 10
-5;
Figure 11 b is the linear DPV response curve of GR-PIL/GCE electrode pair different concns PEA; Wherein, curve a-c represents that respectively the concentration (M) of PEA is: 0,5.0 × 10
-9, 1.0 × 10
-8;
Figure 11 c is the DPV response criteria curve of GR-PIL modified electrode to PEA;
Figure 12 is the selectivity test figure of GR-PIL/GCE electrode;
Figure 13 is preparation and the Electrochemical Detection schema of GR-PIL/GCE electrode; Wherein, GO represents graphene oxide, GR represents Graphene, IL represents ionic liquid, AIBN represents Diisopropyl azodicarboxylate, GR-PIL represents Graphene-poly ion liquid matrix material, GCE represents glass-carbon electrode, Hydrazine represents hydrazine hydrate, GR-PIL droped onto represents " Graphene-poly ion liquid matrix material is dropped to ... ", and absorbing PEA represents " ... absorption Phenylethanolamine A ", and response represents electrochemical reaction, PBS represents phosphoric acid buffer, and DPV singal represents Differential Pulse Voltammetry detection signal.
Embodiment
The preparation of embodiment 1 Graphene-poly ion liquid matrix material
1, graphene oxide is synthetic
Get 0.5g Graphite Powder 99,0.5g NaNO
3, the dense H of 23mL
2sO
4, join successively in 250mL round-bottomed flask, in ice bath, stir 60min; Slowly add again 3g KMnO
4after mixing, in 35 DEG C of oil baths, stir 2 hours; Then, slowly add the water of 40mL, in the time that temperature is elevated to 95 DEG C, stir 30min; Finally, slowly add 100mL water, then add 3mL H
2o
2(30%), suction filtration, uses 1M hydrochloric acid, water washing twice successively, and filtrate is dry at 45 DEG C, obtains graphene oxide (GO).
2, Graphene is synthetic
Getting 0.1g graphene oxide sneaks in 200mL water, after the ultrasonic 2h of 53KHz, add 85% hydrazine hydrate of 100 μ L, 28% strong aqua of 1.4mL, mix and be placed on heated and stirred 60min at 95 DEG C, then water washing, suction filtration, finally vacuum-drying at 60 DEG C, obtains Graphene (GR).
3, Graphene-poly ion liquid matrix material is synthetic
Get 0.02g Graphene and be scattered in 20mL methyl alcohol, after the ultrasonic 30min of 53KHz, add 0.1g1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate, 50mg Diisopropyl azodicarboxylate, more ultrasonic 30min; After inflated with nitrogen 20min, seal flask mouth, in the oil bath of 70 DEG C, react 12h; Reacted rear with ethanol and ultrapure water washing several, vacuum-drying at 70 DEG C, obtains Graphene-poly ion liquid matrix material (GR-PIL).
4, structure and the Performance Detection of Graphene-poly ion liquid matrix material
(1) scanning electron microscope analysis
From Fig. 1 a, graphene oxide (GO) thin slice is laminate structure, and smooth surface; From Fig. 1 b, compared with graphene oxide, it is many that the plicated layer on Graphene (GR) thin slice becomes, and this is owing to the cause of hydrazine reduction; From Fig. 1 c, the surface of Graphene-poly ion liquid matrix material (GR-PIL) presents vesicular structure, and the obvious thickening of GR plicated layer simultaneously shows that grafting of poly ion liquid, to GR surface, illustrates that GR-PIL is successfully prepared.
(2) Infrared spectroscopy
As seen from Figure 2, at 1061cm
-1, 1396cm
-1and 1722cm
-1the characteristic peak at place belongs to graphene oxide, and (curve is the stretching vibration of upper alkoxyl group (C-O), hydroxyl (C-OH), carbonyl (C=O) a), 3426cm
-1locate the stretching vibration peak that strong absorption peak belongs to the upper O-H of GO.
When graphene oxide is after hydrazine hydrate reduction, 3436cm
-1locate strong absorption peak and die down, 1732cm
-1the absorption peak at place disappears; But 1634cm
-1the absorption peak at place still exists, because reduction can not destroy C=C, and 1396cm simultaneously
-1that (curve is the formation vibration peak of the O-H of upper C-OH b) for Graphene.
Compared with GR, (c) there is being positioned at 1559cm in curve to GR-PIL
-1and 1168cm
-1the strong absorption peak at place, these two absorption peaks belong to respectively C=N on imidazoles and the stretching vibration of C-N, also exist the characteristic peak of GR (as 1396cm simultaneously
-1), illustrate that GR-PIL is successfully prepared.
(3) X-ray diffraction analysis
As seen from Figure 3, (curve a) has occurred that in 2 θ=10.5 ° a characteristic peak (a), calculate to such an extent that its interlamellar spacing is 0.842nm according to bragg's formula by curve to GO.
When GO is after hydrazine hydrate reduction, the characteristic diffraction peak of GR moves to right and locates to 2 θ=24.5 °, and (curve b), and strength decreased, this is due to the disappearance of the most of oxy radicals on GO after reduction, finally makes the interlamellar spacing of GR reduce.
Compared with GR, GR-PIL (curve c) in 2 θ=8.4 ° and 21.8 ° locate to have occurred two characteristic diffraction peaks, this is because ion liquid polymerization is behind GR surface, has introduced the other defects such as glyoxaline cation, finally makes interlamellar spacing increase.XRD figure spectrum has also illustrated that RGI-PIL is successfully prepared.
Bragg's formula is: 2dsin θ=n λ;
Wherein, d is spacing, and θ is that diffraction half-angle (θ angle corresponding to diffraction peak occurs, generally 2 θ are called to diffraction angle), n is diffraction progression (be first-order diffraction or the second-order diffraction of a certain crystal face, n generally gets 1), the wavelength that λ is target used.
(4) thermogravimetric analysis (TGA)
As seen from Figure 4, (curve a) has large mass loss to GO between 100～200 DEG C, is mainly derived from the decomposition of oxy radical and carbon skeleton, and loss reaches 75%.Compared with GO, (curve b) has good thermostability to GR, has only lost 30%.And GR-PIL (the curve c) thermostability between 100～200 DEG C is better than GR, but between 300 DEG C～450 DEG C, has larger mass loss, and loss has reached 92%, and this is mainly owing to the thermolysis of PIL.Due to thermostabilitys different between GO, GR, GR-PIL, TGA analysis also further illustrates GR-PIL and successfully prepares.
The preparation of embodiment 2 electrochemical sensors
1, preparation GR-PIL modified electrode
(1) by glass-carbon electrode Al
2o
3powder is outstanding sticks with paste polishing, then uses successively dehydrated alcohol and ultrapure water ultrasonic cleaning, and the frequency of each ultrasonic cleaning is 53KHz, and the time is 5min; Ultrasonic cleaning completes to be placed in air dries, stand-by;
(2) get 5mg Graphene-poly ion liquid matrix material and be scattered in the N of 1mL, in dinethylformamide (concentration of GR-PIL is 5mg/mL), after ultrasonic mixing, get 5 μ L mixing solutionss and drip and be applied to glass-carbon electrode surface, after drying, obtain RGI-PIL modified electrode.
2, the electrochemical behavior analysis of GR-PIL modified electrode to PEA
GR-PIL modified electrode is immersed to blank PBS and contains 1.0 × 10
-5whip attachment 5min in PBS (pH=0.05, the 0.5M NaCl) solution of M PEA, wherein the effect of sodium-chlor is the ionic strength of regulator solution, maintains osmotic pressure.After being fully adsorbed onto on GR-PIL modified electrode, PEA molecule takes out GR-PIL modified electrode, to blank PBS with containing the PBS (pH=0.05 of PEA, 0.5M NaCl) logical nitrogen deoxygenation in solution, and then will GR-PIL modified electrode immerse and in solution, investigate CV (cyclic voltammetry) and DPV (Differential Pulse Voltammetry) responds.
As shown in Figure 5, in blank PBS solution, GR-PIL modified electrode does not occur that (curve a) at redox peak, but when adding after PEA, there is obvious redox peak, in the scanning of first lap, (curve b), there is an irreversible reduction peak at-0.513V, and in reverse scan, there is an oxidation peak at 0.07V place, this is that then azanol base is oxidized to nitroso-group (reaction 2) again because the nitro on PEA is reduced into azanol base (reaction 1).In the second circle scanning (c), reduction peak declines curve, and has occurred that at 0.07V and 0.18V another is to redox peak, this inverse process owing to reaction 2 (reaction 3):
Due to irreversible reduction peak current maximum, our detection signal using this as PEA.In order to obtain highly sensitive, we select DPV to measure PEA reduction peak.
3, the current-responsive analysis of GR-PIL modified electrode to PEA
Fig. 6 is that GR-PIL, PIL (poly ion liquid, 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate), GCE (naked glass-carbon electrode) different modifying electrode are for 1.0 × 10
-5the DPV current-responsive figure of M PEA.As shown in the figure, these electrode pairs PEA has current-responsive, and this is all reduced to azanol base owing to nitro.(c) there is very little reduction peak in curve to GCE at-0.464V place, and when having modified on GCE after PIL (PIL/GCE, b), reduction current has increased curve, and just move to-0.456V of reduction potential place, illustrates that PIL has certain catalytic to PEA.And when introducing after Graphene, under same detection condition, (curve response current a) is larger than PIL/GCE for GR-PIL/GCE, this is because GR-PIL has than PIL/GCE and the better electrochemical behavior of GCE PEA, electrochemical results demonstration, GR-PIL matrix material can improve electronics transfer rate and increase the reduction potential of PEA.
4, the impact of GR-PIL concentration on PEA response current size
To contain 1.0 × 10
-5the PBS (pH=0.05,0.5M NaCl) of M PEA is liquid to be measured, and while analyzing preparation GR-PIL modified electrode, GR-PIL concentration is to PEA (1.0 × 10
-5m) impact of response current size.
As shown in Figure 7, in the time that GR-PIL concentration is increased to 5mg/mL from 1mg/mL (constancy of volume is still 5 μ L), response current increases along with the increase of GR-PIL, and this is owing to the increase of adsorptive power; And in the time that GR-PIL concentration is greater than 5mg/mL, response current starts to decline, this is to have hindered electronics transmission because modified membrane is blocked up.So it is 5mg/mL that the present invention selects the concentration of GR-PIL.
5, the impact of adsorption time on PEA response current size
To contain 1.0 × 10
-5the PBS (pH=0.05,0.5M NaCl) of M PEA is liquid to be measured, the impact of the adsorption time of GR-PIL modified electrode on PEA response current size when analyzing and testing.
As shown in Figure 8, when GR-PIL modified electrode adsorbs 5min in liquid to be measured, it is maximum that response current reaches, and is tending towards afterwards constant.Therefore selecting 5min is herein the optimal adsorption time.
6, the impact of ionogen (PBS) pH on PEA response current size
In order to reach optimum testing conditions, we are also optimized the pH of phosphoric acid buffer.
As shown in Figure 9, the pH of liquid to be measured from 3.0 to 5.0 o'clock, response current increases along with the increase of pH; Be 5.0 o'clock at pH, electric current reaches maximum value; In the time that pH is greater than 5.0, response current starts again to decline, and is 5.0 so select phosphoric acid buffer pH herein.
Shown in Figure 10 is the relation of reduction potential and the pH of GR-PIL modified electrode, and the reduction potential that can find out GR-PIL modified electrode reduces along with the increase of pH and be linear, illustrates that the reaction of electrode surface exists prototropy.
7, the detectability analysis of GR-PIL modified electrode to PEA
The GR-PIL modified electrode preparing is placed in respectively to PBS solution (pH5.0) the absorption 5min containing the PEA of different concns, and reference electrode is Ag/AgCl electrode, is platinum electrode to electrode, and DPV measurement result is as shown in Figure 11 a, 11b, 11c.
The relation of PEA concentration and peak current is as shown in Figure 11 a, 11b, and along with the concentration of PEA increases, current-responsive increases gradually; Typical curve is as shown in Figure 11 c, when PEA concentration is 5.0 × 10
-9～1.0 × 10
-5within the scope of mol/L, PEA concentration (C, 10
-6mol/L) linear with response current (I, μ A), equation of linear regression is:
I (μ A)=0.4386+0.5818C (10
-6mol/L), relation conefficient is 0.9986.Detectability 2.0 × 10
-9mol/L (S/N=3).
8, the selectivity analysis of GR-PIL modified electrode
For the selectivity of inspection GR-PIL modified electrode, using Clenbuterol hydrochloride, Ractopamine hydrochloride, these three kinds of beta-stimulants of salbutamol as interfering substance, at the PEA solution that contains these three kinds of interfering substances (1000 times that concentration is PEA), (PEA concentration is 7.0 × 10 respectively
-6m), in, detect with GR-PIL modified electrode of the present invention and method.
As shown in figure 12, the Clenbuterol hydrochloride, Ractopamine hydrochloride, the salbutamol that in PEA solution, contain do not have interference substantially to the detected result of PEA; Show that GR-PIL modified electrode of the present invention has high sensitivity to PEA, is suitable for the detection of PEA in actual sample.
Embodiment 3 utilizes GR-PIL modified electrode to carry out actual sample detection
For investigating the reliability of this GR-PIL modified electrode, actual sample is detected.
For Pig Liver or pork sample, pre-treating process is:
(1) Pig Liver 1.0g being ground or pork sample and 5mL ethyl acetate and 0.6mL10%Na
2cO
3solution stirring is mixed, then centrifugal under the speed of 3500r/min, collected organic layer;
(2) repeating step (1) twice;
(3) in the organic layer of collecting out, add 1mL0.1M HCl, thermal agitation 2min, more centrifugal 5min, collect lower floor's material;
(4) repeating step (3) twice, collects extracting solution;
(5) with PBS damping fluid (pH5.0), extracting solution is diluted to 10mL; Before detection, add the PEA that determines concentration, make mark-on sample.
For pig urine samples, its pre-treating process is: pig is urinated with the centrifugal 10min of 8000r/min, remove bottom centrifugal go out albumen and impurity; The pig urine on upper strata with PBS (pH=5.0) be diluted to 100 times for subsequent use, each sample is distinguished replicate(determination) five times; Before detection, add the PEA that determines concentration, make mark-on sample.
GR-PIL modified electrode is immersed in each mark-on sample and taken out after whip attachment 5min, to logical nitrogen deoxygenation in each mark-on sample, and then modified electrode is placed in to each mark-on sample and carries out the Electrochemical Detection of DPV, detected result is as shown in table 1:
Table 1
From table 1, GR-PIL modified electrode of the present invention is to the rate of recovery of PEA at 98.2%-103.8%, and relative standard deviation is at 3.8%-4.8%.Therefore GR-PIL modified electrode of the present invention and detection method have feasibility in actual sample analysis.
Claims (9)
1. a preparation method for Graphene-poly ion liquid matrix material, comprising:
Under protection of inert gas, Graphene and ionic liquid with ethylene linkage are carried out to Raolical polymerizable under initiator exists, after react through washing, the described Graphene-poly ion liquid matrix material of dry acquisition.
2. preparation method as claimed in claim 1, is characterized in that, described rare gas element is nitrogen, argon gas or helium.
3. preparation method as claimed in claim 1, is characterized in that, the described ionic liquid with ethylene linkage is 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate, 1-allyl group-3-ethyl imidazol(e) phosphofluoric acid hydrochloride or 1-allyl group-3-Methylimidazole villaumite.
4. preparation method as claimed in claim 3, is characterized in that, the mass ratio of Graphene and 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate is 1:2～20.
5. preparation method as claimed in claim 1, is characterized in that, described initiator is Diisopropyl azodicarboxylate, Potassium Persulphate or ammonium persulphate.
6. preparation method as claimed in claim 1, is characterized in that, the condition of described Raolical polymerizable is: 60～80 DEG C of temperature of reaction, reaction times 6～18h.
7. Graphene-poly ion liquid the matrix material making by preparation method as described in as arbitrary in claim 1～6.
8. an electrochemical sensor, comprises working electrode, it is characterized in that, the surface of described working electrode is coated with Graphene-poly ion liquid matrix material as claimed in claim 7.
9. the application of electrochemical sensor in detection Phenylethanolamine A as claimed in claim 8.
Priority Applications (1)
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