CN103018304B - Glass-carbon electrode that a kind of nickel oxide-graphene nano material is modified and its preparation method and application - Google Patents
Glass-carbon electrode that a kind of nickel oxide-graphene nano material is modified and its preparation method and application Download PDFInfo
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- CN103018304B CN103018304B CN201310005619.7A CN201310005619A CN103018304B CN 103018304 B CN103018304 B CN 103018304B CN 201310005619 A CN201310005619 A CN 201310005619A CN 103018304 B CN103018304 B CN 103018304B
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Abstract
The invention belongs to galvanochemistry and technical field of nano material, the detection of paracetamol is used in particular to a kind of glass-carbon electrode based on the modification of nickel oxide-graphene nano material and preparation method thereof and this electrode, first by graphene oxide ultrasonic disperse in ultrapure water, obtain graphene oxide colloidal solution, then obtained graphene oxide colloidal solution and nickel sulfate solution is ultrasonic is mixed and made into electrolytic solution; In electrolytic solution obtained by cleaner electrode being immersed, dry after electrode surface even constant potential electro-deposition Graphene and nickel oxide, wash, obtain required glass-carbon electrode.The preparation technology of this glass-carbon electrode is simple, preparation time is short, asepsis environment-protecting, and cost is low.And described glass-carbon electrode can be used for the detection of paracetamol, and the tool response time is fast, the range of linearity is wide, favorable reproducibility, stability are high, and the interference of the electroactive material do not coexisted, and is a kind of excellent detecting electrode.
Description
Technical field
The invention belongs to galvanochemistry and technical field of nano material, particularly a kind of glass-carbon electrode based on the modification of nickel oxide-graphene nano material and preparation method thereof and this electrode are used for the detection of paracetamol.
Background technology
Paracetamol (paracetamol, acetaminophen, acetaminophen), has antipyretic effect, for cat fever, arthralgia, neuralgia, antimigraine, pain caused by cancer and postoperative analgesia etc.But excessive use paracetamol can cause liver damage, it is even dead that severe patient can cause stupor.The hepatotoxicity wind agitation of paracetamol comes from produced problem in drug metabolism processes; in biotransformation, it can produce a kind of metabolite, i.e. N-acetyl 1,4-benzoquinone imines; its characteristic is comparatively large, needs the protective factors such as the reductive glutathione in body to be combined and could to reduce toxicity.If it is excessive to take paracetamol dosage, or when the protective factors such as glutathione reduces, causes the important large molecule of the larger intermediate metabolites of this toxicity and other to be combined, just there will be hepatic injury.Therefore, a kind of reliable, quick and economic method detects paracetamol accurately and has great importance.The detection method of paracetamol has a lot, such as: analysis by titration, spectrophotometric method, chemoluminescence method and electrochemical method.But, in these methods, electrochemical method has the advantage such as short consuming time of pretreatment work before easy, accurate, highly sensitive, the low detection of cost because of it, is widely used in the detection of paracetamol, so the stability of detecting electrode and reappearance are vital to testing result.But the detecting electrode reappearance of sensor used is at present poor, the response time is slower.
Nano particle plays a very important role because it has larger specific surface area, good conductivity and biocompatibility tool in raising sensor performance.Especially metal or metal oxide nanoparticles cause the great interest of researcher, and they utilize gold, carbon nano-tube and other nano particles to build acetparaminosalol phenol sensor.Meanwhile, Graphene enjoys liking of researcher due to the structure of its uniqueness, high physical strength, tuneable optical property and electric conductivity.But traditional preparation method, especially chemical reduction method often causes the pollution of product.Because chemical reduction method often uses the poisonous or expensive reagent such as hydrazine or sodium borohydride as reductive agent.Therefore, developing a kind of green method preparing Graphene is significantly.Research in recent years shows, the method that Direct electrochemical reduction graphene oxide prepares Graphene is very effective, and the Graphene of electrochemical reduction has been applied to many fields: as sensor, capacitor and fuel cell etc.
Summary of the invention
The object of this invention is to provide the glass-carbon electrode that a kind of nickel oxide-graphene nano material is modified, this electrode has for the detection of paracetamol the catalytic oxidation activity that the response time is short, favorable reproducibility, stability are high and good.
Another object of the present invention is to provide the preparation method of the glass-carbon electrode that a kind of above-mentioned nickel oxide-graphene nano material is modified.
Object of the present invention can be realized by following scheme:
Prepare a method for the glass-carbon electrode that nickel oxide-graphene nano material is modified, its step comprises:
(1) by graphene oxide ultrasonic disperse in ultrapure water, obtain graphene oxide colloidal solution, then obtained graphene oxide colloidal solution and NiSO
46H
2o solution is ultrasonic is mixed and made into electrolytic solution;
(2) clean electrode is immersed in electrolytic solution obtained in step (1), dry after electrode surface constant potential electro-deposition Graphene and nickel oxide, wash.Preferably, first by the electrode aluminium powder of 0.3 μm polishing, then ultrasonic process 3-5 minute in ultrapure water, absolute ethyl alcohol, ultrapure water successively, namely obtains clean electrode after drying.
In the electrolytic solution of described step (1), the proportioning of graphene oxide and Ni ion is 1g:3-20mmol.Preferably, in the electrolytic solution in described step (1), the proportioning of graphene oxide and Ni ion is 1g:5-10mmol.
The graphene oxide content of the electrolytic solution in described step (1) is 1 ~ 4mg/ml.
Also containing 0.02 ~ 0.05mol/L sodium sulphate in electrolytic solution in described step (1).
In described step (2), potentiostatic electrodeposition current potential used is-1.0 ~-1.8V, and the potentiostatic electrodeposition time used is 50 ~ 2100 seconds.Preferably, potentiostatic electrodeposition current potential used is-1.5V, and the potentiostatic electrodeposition time used is 150-200 second.
The invention still further relates to the application of glass-carbon electrode in detection paracetamol that nickel oxide-graphene nano material is modified.
Graphene oxide used in the present invention adopts improvement Hummers method to prepare.
The invention has the beneficial effects as follows: 1, the preparation method of the glass-carbon electrode of described nickel oxide-graphene nano material modification adopts galvanochemistry one stage reduction method to obtain, and preparation technology is simple, preparation time is short, asepsis environment-protecting, and cost is low.2, the even electro-deposition of described glass-carbon electrode outside surface has Graphene and nickel oxide, can be used for the detection of paracetamol, and it is active to go out good catalytic oxidation to the detected representation of paracetamol, and the tool response time is fast, the range of linearity is wide, favorable reproducibility, stability are high, and the interference of the electroactive material do not coexisted, paracetamol is detected and is limited to 2 × 10
-8mol/L is a kind of excellent detecting electrode.
Accompanying drawing explanation
Fig. 1 is nickel oxide-graphene nano particle (a), and the Raman spectrogram of Graphene (b) prepared by electrochemical reducing and graphene oxide (c), interior illustration is the raman signatures spectrum of nickel oxide.
Fig. 2 is the field emission scanning electron microscope figure of the glass-carbon electrode that nickel oxide-graphene nano material is modified.
Fig. 3 is the photoelectron spectroscopy figure of the glass-carbon electrode that nickel oxide-graphene nano material is modified.
Fig. 4 is photoelectron spectroscopy figure (a) of graphene oxide, photoelectron spectroscopy figure (b) of Graphene prepared by electrochemical reducing.
Fig. 5 is the photoelectron spectroscopy figure of electro-deposition gained nickel oxide.
Fig. 6 is that the glass-carbon electrode of nickel oxide-graphene nano material modification is to the cyclic voltammogram of paracetamol.
Fig. 7 be nickel oxide-graphene nano material modify glass-carbon electrode to the differentiated pulse volt-ampere curve figure of paracetamol, interior illustration is the peak current of this glass-carbon electrode to the detection of paracetamol and the graph of a relation of concentration.
Fig. 8 be nickel oxide-graphene nano material modify glass-carbon electrode and common graphite alkene glass-carbon electrode to the differentiated pulse volt-ampere curve figure of the interference test of paracetamol.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Equipment used by the present embodiment: the shooting of Hitachi S-4800 type scanning electron microscope, pHS-3C acidity meter for laboratory, KQ3200E type ultrasonic cleaner, PHI5000ESCA x-ray photoelectron spectroscopy, LabRam Π, Dilor(France) spectrometer.
Embodiment 1
By the glass-carbon electrode aluminium powder of 0.3 μm polishing, more successively at ultrapure water, absolute ethyl alcohol, ultrasonic process 3-5 minute in ultrapure water, the glass carbon of obtained cleaning, then dries, for subsequent use at ambient temperature;
Taking 4mg graphene oxide (this graphene oxide adopts the synthesis of Hummers method) is dissolved in 1ml ultrapure water, and ultrasonic process 6 hours, makes graphene oxide be dispersed in ultrapure water, obtains the graphene oxide colloidal solution that concentration is 4mg/mL;
Be the NiSO of 40mmol/L by concentration
46H
2o solution (the Na wherein containing 0.1mol/L in solution
2sO
4as supporting electrolyte) and the graphene oxide colloidal solution of above-mentioned preparation take volume ratio as the ratio mixing of 1:1.5, ultrasonic process 5 minutes, obtained electrolytic solution; Be immersed in this electrolytic solution by the clean glass-carbon electrode processed, under-1.5V constant potential, electro-deposition 150 seconds, then dries glass-carbon electrode in air, washing, obtains the glass-carbon electrode that nickel oxide-graphene nano material is modified.
Embodiment 2
By the glass-carbon electrode aluminium powder of 0.3 μm polishing, more successively at ultrapure water, absolute ethyl alcohol, ultrasonic process 3-5 minute in ultrapure water, the glass carbon of obtained cleaning, then dries, for subsequent use at ambient temperature;
Taking 5mg graphene oxide (this graphene oxide adopts the synthesis of Hummers method) is dissolved in 1mL ultrapure water, and ultrasonic process 6.5 hours, makes graphene oxide be dispersed in ultrapure water, obtains the graphene oxide colloidal solution that concentration is 5mg/mL;
Be the NiSO of 50mmol/L by concentration
46H
2o solution (the Na wherein containing 0.1mol/L in solution
2sO
4as supporting electrolyte) and the graphene oxide colloidal solution of above-mentioned preparation take volume ratio as the ratio mixing of 1:2, ultrasonic process 5 minutes, obtained electrolytic solution; Be immersed in this electrolytic solution by the clean glass-carbon electrode processed, under-1.5V constant potential, electro-deposition 200 seconds, then dries glass-carbon electrode in air, washing, obtains the glass-carbon electrode that nickel oxide-graphene nano material is modified.
Performance characterization: the glass-carbon electrode that the nickel oxide-graphene nano material used by following test is modified is the glass-carbon electrode prepared in embodiment 1.
(1), Raman spectrum detects
Nickel oxide-graphene nano particle is carried out Raman spectrum detection, Raman spectrogram is as a in Fig. 1, simultaneously again by the Graphene of electrochemical process reduction, Raman spectrogram is as the b in Fig. 1 and the graphene oxide adopting the synthesis of Hummers method, Raman spectrogram such as the c in Fig. 1 compares, and result shows: the Graphene of graphene oxide and electrochemical process reduction all show stronger D peak (due to the defect peak that intervalley scattering is formed) and strong G peak.But the Graphene that electrochemical process is reduced compared with graphene oxide shows a slightly strong 2D peak.And the intensity of the D/G of the Graphene of electrochemical process reduction is greater than graphene oxide, shows thus to increase at the number of electrochemical reduction Graphene smaller size particles.These all illustrate that graphene oxide is successfully reduced to Graphene.Further, in a of Fig. 1, we can observe at 400-500cm
-1there is the raman signatures spectrum of nickel oxide in scope, the existence of nickel oxide is described, specifically see the interior illustration in Fig. 1.
(2), the glassy carbon electrode surface shape appearance figure of nickel oxide-graphene nano material modification
Field emission scanning electron microscope is a kind of means that can be used for characterizing electrode surface pattern.Adopt the surface topography of field emission scanning electron microscope shooting glass-carbon electrode, specifically as shown in Figure 2, can observe from Fig. 2, nickel oxide is evenly distributed on glass-carbon electrode, and the Graphene not occurring to reunite covers on nickel oxide surfaces.
(3), the composition detection of the glass-carbon electrode of nickel oxide-graphene nano material modification
Can see from x-ray photoelectron spectroscopy (XPS) figure shown in Fig. 3, the glass-carbon electrode that prepared nickel oxide-graphene nano material is modified only has 3 kinds of element compositions: carbon, oxygen, nickel.
Graphene and nickel oxide compound to characterize prepared material further, the Graphene of x-ray photoelectron power spectrum to graphene oxide and electrochemical process reduction is adopted to characterize, specifically as shown in Figure 4, Fig. 4 a is the XPS figure of graphite oxide, Fig. 4 b is that the XPS of the Graphene of electrochemical process reduction schemes.Result surface: graphene oxide C1s photoelectron spectroscopy figure in oxygen-containing functional group containing obvious very large and degree of oxidation, belong to the different functional groups of carbon respectively: the ring-type carbon of anaerobic, epoxy carbon, hydroxyl carbon and carbonyl carbon.Although, also there is identical functional group in the Graphene of electrochemical process reduction, but their peak intensity is significantly weak than graphene oxide.Thus, the method for electrochemical reduction, provides a kind of feasible method preparing graphene film on electrode.
Adopt the XPS map analysis valence state of nickel, specifically as shown in Figure 5, the Ni(2p of the nickel oxide (NiO) in Fig. 5) integrate features can be as follows: 855.8eV(2p
3/2), 861.6eV (2p
3/2), 873.6eV (2p
1/2) and 879.0eV (2p
1/2), show the existence of nickel oxide, and testing result is also corresponding with the Raman spectrogram in Fig. 1.
(4), the glass-carbon electrode of nickel oxide-graphene nano material modification is to the detection of paracetamol (AP)
A, electrocatalysis characteristic
The glass-carbon electrode modified by the nickel oxide-graphene nano material of preparation has carried out electro-catalysis test to the AP solution that concentration is 1mmol/L, specifically see Fig. 6, there is no the PBS(pH=7.0 of AP) solution in be a level and smooth curve, as shown in a detection line in figure, when adding after concentration is the AP of 1mmol/L, a pair obvious redox peak can be observed occur, as shown in the b detection line in figure, it can thus be appreciated that: the glass-carbon electrode that nickel oxide-graphene nano material is modified has good catalytic performance to AP.
B, detectability
Adopt Differential Pulse Voltammetry, the glass-carbon electrode that test nickel oxide-graphene nano material is modified is to the detectability of AP and the range of linearity, and concrete test result as shown in Figure 7, is 2 × 10 in concentration
-8mol/L to 1 × 10
-4within the scope of mol/L, prepared glass-carbon electrode has well linear to AP, detect and be limited to 2 × 10
-8mol/L.
C, selectivity and disturbed test
In the analysis design mothod of actual sample, some electroactive materials coexisted may disturb the testing result to AP, so carried out selectivity and interference experiment.The glass-carbon electrode that nickel oxide-graphene nano material is modified is tested as agent interfering adding dopamine, ascorbic acid and uric acid in AP testing process respectively, and adds the dopamine of same concentrations, ascorbic acid and uric acid when detecting AP with common Graphene electrodes and test as a comparison.Concrete outcome is as follows:
At the glass-carbon electrode utilizing nickel oxide-graphene nano material to modify in AP testing process, add concentration and be the dopamine of 0.1mmol/L, ascorbic acid and uric acid, but AP is detected and does not cause obvious interference, as shown in a detection line of Fig. 8, and compared with detected peaks when utilizing common Graphene electrodes to detect AP (the b detection line of Fig. 8), peak obviously becomes by force large, and the glass-carbon electrode prepared by explanation detects AP and has good selectivity.
Simultaneously, also the AP content in actual sample (day and night hundred clothes are given repeated exhortations) is measured, result is as shown in table 1, day, the sheet recovery was 95.93% ~ 103.5%, the relative standard deviation (RSD) measured for 5 times is 3.373%, because sheet at night many a kind of compositions of chlorphenamine maleate compared with day sheet, thus corresponding analysis has also been carried out to sheet at night, result shows: the detection of chlorphenamine maleate to AP is not disturbed, night, the recovery of sheet was 98.24% ~ 102.4%, RSD=2.079%(n=5), illustrate that this glass-carbon electrode is very high to the Detection accuracy of AP.
Table 1
D, stability test
The glass-carbon electrode that same nickel oxide-graphene nano material is modified is carried out 5 parallel experiments to the AP that concentration is 1mmol/L, the relative standard deviation that result shows these 5 times experiments is less than 1.489%, prepare the AP that 5 identical electrodes detect 1mmol/L simultaneously, relative standard deviation is 2.622%, and the above results describes this glass-carbon electrode and has good reappearance.This glass-carbon electrode is preserved at normal temperatures and is measured the AP that concentration is 1mmol/L for every 5 days, find after one month that the peak current of this glass-carbon electrode is original 91.40%, the glass-carbon electrode describing the nickel oxide-graphene nano material modification adopting this law to prepare thus has good stability.
Claims (7)
1. the glass-carbon electrode of a nickel oxide-graphene nano material modification, it is characterized in that: have nickel oxide and graphene nano particle in the even electro-deposition of glass-carbon electrode outside surface, the glass-carbon electrode that described nickel oxide-graphene nano material is modified adopts following methods preparation:
(1) by graphene oxide ultrasonic disperse in ultrapure water, obtain graphene oxide colloidal solution, then obtained graphene oxide colloidal solution and nickel sulfate solution is ultrasonic is mixed and made into electrolytic solution; In this electrolytic solution, the proportioning of graphene oxide and Ni ion is 1g:3-20mmol;
(2) clean electrode is immersed in electrolytic solution obtained in step (1), dry after electrode surface constant potential electro-deposition Graphene and nickel oxide, wash; Potentiostatic electrodeposition current potential used is-1.0 ~-1.8V, and the potentiostatic electrodeposition time used is 50 ~ 2100 seconds.
2. the glass-carbon electrode of nickel oxide-graphene nano material modification according to claim 1, is characterized in that: the graphene oxide of the electrolytic solution in described step (1) and the proportioning of Ni ion are 1g:5-10mmol.
3. the glass-carbon electrode of nickel oxide-graphene nano material modification according to claim 1, is characterized in that: the graphene oxide content of the electrolytic solution in described step (1) is 1 ~ 4mg/mL.
4. the glass-carbon electrode of nickel oxide-graphene nano material modification according to claim 1, is characterized in that: also containing 0.02 ~ 0.05mol/L sodium sulphate in the electrolytic solution in described step (1).
5. the glass-carbon electrode of nickel oxide-graphene nano material modification according to claim 1, it is characterized in that: in described step (2), potentiostatic electrodeposition current potential used is-1.5V, and the potentiostatic electrodeposition time used is 150-200 second.
6. the glass-carbon electrode of nickel oxide-graphene nano material modification according to claim 1, it is characterized in that: in described step (2), first by the aluminium powder polishing of electrode with 0.3 μm, then ultrasonic process 3-5 minute in ultrapure water, absolute ethyl alcohol, ultrapure water successively, namely obtains clean electrode after drying.
7. the glass-carbon electrode that nickel oxide-graphene nano material according to claim 1 is modified is detecting the application in paracetamol.
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