CN103235019A - Cyclodextrin/grapheme nanometer compound modified electrode, preparation method and usage - Google Patents
Cyclodextrin/grapheme nanometer compound modified electrode, preparation method and usage Download PDFInfo
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Abstract
The invention relates to a preparation of cyclodextrin/grapheme nanometer compound modified electrode and simultaneous usage in trace quantity detection of heavy metal ions, and belongs to the fields of nanocomposite and environment monitoring. The invention mainly employs cyclodextrin/grapheme nanometer compound modified glassy carbon electrode as a working electrode, and a saturated calomel electrode as a reference electrode, a platinum wire electrode as a counter electrode, and simultaneously carries out a quantitative analysis determination of trace quantity heavy metal ions by a square wave anodic stripping voltammetry. The electrode prepared by the invention has the advantages of good electrode reappearance and stability, simple and rapid operation process, and substantially improves the detection sensitivity and the limiting value of the detected heavy metal ions reaches to 10-11 M level.
Description
Technical field:
The invention belongs to nano composite material and environmental monitoring field, the preparation method who is specifically related to a kind of cyclodextrin/graphene nanometer composite modified glassy carbon electrode reaches for detection of the trace heavy metal ion.
Background technology:
Along with developing rapidly of industrial or agricultural, the pollution of heavy metal ion is aggravation year by year.Heavy metal not only can exist in the environment midium or long term, also can be by food chain enrichment in people and animal and plant body.In recent years, heavy metal pollution has caused great attention because it is on the rise to the threat that environment and human health cause in worldwide.
At present, the method for detection heavy metal ion mainly comprises: atomic absorption spectrography (AAS), fluorescent spectrometry, inductivity coupled plasma mass spectrometry analytic approach and electrochemical methods.Compare with classic method, electrochemical methods is easy because of it, fast, and sensitivity, advantage such as accurate and obtained using widely.The anodic stripping voltammetry (Anodic Stripping Voltammetry ASV) that the present invention is based in the electrochemical methods detects.It mainly comprises deposition and two processes of stripping, at first, will be detected ion on the surface of certain potentials deposit reduction at working electrode that is:.Then, during the reverse scan electrode potential, the material generation oxidation reaction that has deposited and the stripping volt-ampere curve is recorded in stripping simultaneously.The electroactive of inductive material depended in the sensitivity of anodic stripping voltammetry, so the present invention adopts graphene complex to carry out modified electrode.
Graphene is a kind of by sp
2The hydridization carbon atom is piled up the new carbon of the bi-dimensional cellular shape crystalline network that forms, and its thickness is 0.35nm only, is the thinnest in the world two-dimensional material.To have specific surface area big because of it for Graphene, carrier mobility is fast, physics, the chemical property of good heat conductivity and the high excellence of physical strength, and at advanced composite material (ACM), photoelectric functional material and device, aspects such as solar cell and sensor material have a wide range of applications.But the reunion of Graphene reduces its specific surface area, further reduces its adsorptive power, has limited its further widespread use.The present invention comes grapheme modified with cyclodextrin, not only overcome the influence of reuniting, and has also increased its selection and adsorptive power to heavy metal ion simultaneously.As inductive material, invented a kind of detection soon with this nano-complex, highly sensitive, the method for detection trace heavy metal ion in the time of favorable reproducibility, and this method is nontoxic to environment and human health.
Summary of the invention:
The object of the present invention is to provide the method for a kind of cyclodextrin/graphene nanometer composite modified glassy carbon electrode and detection trace heavy metal ion, specifically comprise the preparation of cyclodextrin/graphene nanometer composite modified glassy carbon electrode, and with this electrode as working electrode, adopting the saturated calomel electrode of buying simultaneously is contrast electrode, platinum electrode is to electrode, finishes trace detection to heavy metal ion by the three-electrode system that constitutes.Adopt the square wave anodic stripping voltammetry in the testing process.
The preparation method of a kind of cyclodextrin of the present invention/graphene nanometer composite modified glassy carbon electrode comprises the steps:
1. the pre-service of glass-carbon electrode: with glass-carbon electrode (3 millimeters of diameters) at the Al of polishing cloth with 0.05 micron
2O
3Powder is polished to minute surface.Absolute ethyl alcohol, ultrapure water ultrasonic cleaning 5 minutes are used in the ultrasonic cleaning 2 minutes in ultrapure water earlier of polishing back more successively, dry up with nitrogen at last, and are stand-by.
2. the preparation of cyclodextrin/graphene nanometer composite modified glassy carbon electrode:
At first, utilize improved Hummers method to prepare graphene oxide by oxidation, mechanical stripping, the flocculation drying and other steps of graphite.The concrete operations step is as follows: adding 10-100 milliliter mass concentration in 50-5000 milliliter round-bottomed flask is that the 95-98% concentrated sulphuric acid and 20-100 milliliter mass concentration are the red fuming nitric acid (RFNA) of 65-68%, stirred 5-50 minute at 0 ℃ of condition of ice bath lower magnetic force, add 2-200 gram natural flake graphite then, vigorous stirring prevents from reuniting, after waiting to be uniformly dispersed, add 10-100 gram potash chlorate, remove at last under the ice bath room temperature and reacted 20-150 hour, after question response is finished, with the product washing, ultrasonic peeling off is with the NaOH flocculation and in 20-80 ℃ of dry 2-10 hour, grind, get the graphene oxide pressed powder.
Graphene oxide is dissolved in the deionized water, add excessive hydroxypropyl-
-cyclodextrin, ultrasonic dispersion 10-60 minute, the auxiliary reaction down of microwave 10 minutes-2 hours, microwave power was 100-800 watt, and temperature of reaction is 20-80 ℃, add reductive agent subsequently, reacted 10-120 minute down in 50-100 ℃, after reaction finishes, centrifugal under 3000-10000 rev/min rotating speed, and use the absolute ethyl alcohol cyclic washing, with remove unreacted hydroxypropyl-
-cyclodextrin in 30-120 ℃ of following vacuum drying 2-20 hour, namely gets product cyclodextrin/graphene nanometer composite at last.
Cyclodextrin/graphene nanometer composite dissolution with solvents that above-mentioned steps is made, controlling its concentration is the 0.5-50 mg/ml, add 5% the Nafion of cyclodextrin/graphene nanometer composite liquor capacity 0.1-10% again, ultrasonic dispersion 10-60 minute, obtain uniform dispersion liquid.Pipette the above-mentioned dispersion liquid of 3-10 microlitre with the micropipette rifle, drip and to be coated in the glass-carbon electrode surface of handling well, dry under the room temperature, obtain the electrode that cyclodextrin/graphene nanometer composite is modified.In order to contrast, preparation Graphene modified glassy carbon electrode and cyclodextrin modified glass-carbon electrode use the same method.
The present invention also provides a kind of method that detects the trace heavy metal ion, is applicable to the trace detection of heavy metal ion in environment measuring and the water analysis.Its concrete assay method is as follows: be to electrode as working electrode, saturated calomel electrode as contrast electrode, platinum electrode with the cyclodextrin/graphene nanometer composite modified electrode of above-mentioned preparation, constitute three-electrode system thus.When measuring heavy metal ion, it is the buffer solution of 3.0-6.0 that three-electrode system is placed 20 milliliters 0.1 mol pH earlier, scans for several times until obtaining level and smooth curve, with the activation of the electrode surface of finishing the work with cyclic voltammetry.Then under stirring condition, in above-mentioned buffer solution, add certain density heavy metal ion solution successively with the micropipette rifle, enrichment 30-600 second under current potential-0.4～-1.8 volt, use the reverse scan of square wave anodic stripping voltammetry then, record the stripping volt-ampere curve simultaneously.
The used reductive agent of the present invention is one or more in ammoniacal liquor, hydrazine hydrate, NaOH, sodium borohydride and the vitamin C.
Solvent for use of the present invention is deionized water, ethanol, acetone, N, one or more in the dinethylformamide.
The used buffer solution of the present invention is a kind of in acetic acid-sodium acetate, ammonium chloride-hydrochloric acid, the disodium-hydrogen-sodium dihydrogen phosphate buffer.
The used heavy metal ion solution of the present invention is one or more in lead, cadmium, mercury, silver, chromium, copper, zinc, the bismuth solution.
Beneficial effect of the present invention is as described below:
The nano-complex of cyclodextrin/Graphene provided by the invention has possessed the electric conductivity, big specific surface area of excellence of host-guest recognition capability, enrichment performance and the Graphene of cyclodextrin simultaneously.The modification of water soluble Beta-cyclodextrin molecule has not only overcome the reunion of Graphene, more is conducive to the selectivity of heavy metal ion is caught.
In addition, the present invention is by the galvanochemistry stripping voltammetry, be that working electrode detects simultaneously to the trace heavy metal ion with cyclodextrin/graphene nanometer composite modified glassy carbon, operating process is simple, quick, detection method reappearance, good stability, and improved the sensitivity that detects greatly.The modification of cyclodextrin has the detection limit of good detection effect, especially lead ion and cadmium ion to reach 9.42 * 10 respectively to heavy metal ion
-11Mol and 6.73 * 10
-11Mol.
Description of drawings:
Interaction synoptic diagram between the composition principle of Fig. 1 cyclodextrin/graphene nanometer composite and this compound and the heavy metal ion.
The transmission electron microscope picture of Fig. 2 graphene oxide (a) and cyclodextrin/graphene nanometer composite (b).
The thermogravimetric curve figure of Fig. 3 Graphene, graphene oxide, cyclodextrin, cyclodextrin/graphene nanometer composite.
Fig. 4 is containing plumbous and cadmium (1.0 * 10
-7Mol) in 0.1 mol pH, 4.5 acetic acid-sodium acetate buffer solution, naked glass-carbon electrode, Graphene modified glassy carbon electrode, the square wave anodic stripping voltammetry figure of cyclodextrin modified glass-carbon electrode and cyclodextrin/graphene nanometer composite modified glassy carbon electrode.
The square wave anodic stripping voltammetry figure (a) of the multiple lead at different concentrations of Fig. 5 and cadmium solution, the concentration of the big or small characterizing metal ion of peak current.Peak current and (b) lead and (c) linear relationship chart of concentration of cadmium ions.
Embodiment:
The present invention is described in further detail below by the drawings and specific embodiments.
Embodiment 1The first step, the i.e. preparation of cyclodextrin/graphene nanometer composite modified glassy carbon electrode.
(1) pre-service of glass-carbon electrode: with glass-carbon electrode (3 millimeters of diameters) at the Al of polishing cloth with 0.05 micron
2O
3Powder is polished to minute surface.Polishing back in ultrapure water ultrasonic 2 minutes is earlier used absolute ethyl alcohol, ultrapure water ultrasonic cleaning 5 minutes more successively, dries up with nitrogen at last, and is stand-by.
(2) preparation of cyclodextrin/graphene nanometer composite modified glassy carbon electrode:
At first, utilize improved Hummers method to prepare graphene oxide by oxidation, mechanical stripping, the flocculation drying and other steps of graphite.The concrete operations step is as follows: add the 72 milliliters of concentrated sulphuric acid and 36 milliliters of red fuming nitric acid (RFNA)s that mass concentration is 65-68% that mass concentration is 95-98% in 500 milliliters of round-bottomed flasks, stirred 15 minutes at 0 ℃ of condition of ice bath lower magnetic force, add 4 gram natural flake graphites then, vigorous stirring prevents from reuniting, after waiting to be uniformly dispersed, add 44 gram potash chlorate, remove at last under the ice bath room temperature and reacted 96 hours.After question response was finished, with the product washing, ultrasonic peeling off got the graphene oxide pressed powder in 6 hours with the NaOH flocculation and in 40 ℃ of dryings.
Take by weighing 40 milligrams of graphene oxides and be dissolved in 80 ml deionized water, add again 1.0 the gram hydroxypropyls-
-cyclodextrin, ultrasonic dispersion 20 minutes; The auxiliary reaction down of microwave 30 minutes, microwave power was 450 watts, and temperature of reaction is 50 ℃; Add 500 microlitre ammoniacal liquor and 100 microlitre hydrazine hydrates subsequently, reacted 30 minutes down in 75 ℃, after reaction finishes, potpourri is poured in the centrifuge tube, under 8000 rev/mins rotating speed centrifugal 15 minutes, and with a large amount of absolute ethyl alcohol cyclic washings, with remove unreacted hydroxypropyl-
-cyclodextrin in 70 ℃ of following vacuum drying 6 hours, namely gets product cyclodextrin/graphene nanometer composite at last.Its preparation principle is seen Fig. 1, and pattern and thermal stability are seen Fig. 2 and Fig. 3 respectively.
With 1 milliliter of N of 1 milligram of usefulness of cyclodextrin/graphene nanometer composite that above-mentioned steps makes, dinethylformamide dissolves, and adds the Nafion of 20 microlitres 5% again, and ultrasonic dispersion obtains uniform dispersion liquid.Pipette the above-mentioned dispersion liquid of 5 microlitres with the micropipette rifle, drip and to be coated in the glass-carbon electrode surface of handling well, dry under the room temperature, obtain the electrode that cyclodextrin/graphene nanometer composite is modified.In order to contrast, preparation Graphene modified glassy carbon electrode and cyclodextrin modified glass-carbon electrode use the same method.As shown in Figure 4, the cyclodextrin/performance of graphene nanometer composite modified glassy carbon electrode is better than other electrode far away.
Second step. be the detection that cyclodextrin/graphene nanometer composite modified glassy carbon electrode is used for heavy metal ion.As working electrode, saturated calomel electrode is to electrode as contrast electrode, platinum electrode, constitutes three-electrode system thus with the cyclodextrin/graphene nanometer composite modified glassy carbon electrode of above-mentioned preparation.When measuring heavy metal ion, it is acetic acid-sodium acetate buffer solution of 4.5 that three-electrode system is placed 20 milliliter of 0.1 mol pH earlier, with cyclic voltammetry with 300 millivolts/second velocity sweeping for several times until obtaining level and smooth curve, with the activation of the electrode surface of finishing the work.Then under stirring condition, the lead and the cadmium standard solution that add a certain amount of variable concentrations with the micropipette rifle in the above-mentioned solution successively, enrichment 120 seconds under current potential-1.2 volt is then recorded the stripping volt-ampere curve simultaneously with the reverse scan of square wave anodic stripping voltammetry.
Embodiment 2 presses the preparation method of embodiment 1, just changes described reductive agent into sodium hydroxide solution and sodium borohydride by ammoniacal liquor and hydrazine hydrate, obtains the result shown in Fig. 2,3 equally.
Embodiment 3 presses the preparation method of embodiment 1, just makes described reductive agent into sodium borohydride by ammoniacal liquor and hydrazine hydrate, obtains the result shown in Fig. 2,3 equally.
Embodiment 4 presses the preparation method of embodiment 1, just changes described reductive agent into sodium hydroxide solution and vitamin C by ammoniacal liquor and hydrazine hydrate, obtains the result shown in Fig. 2,3 equally.
Embodiment 5 presses the preparation method of embodiment 1, just changes described reductive agent into vitamin C by ammoniacal liquor and hydrazine hydrate, obtains the result shown in Fig. 2,3 equally.
Embodiment 7 presses the method for embodiment 1, just with described solvent by N, dinethylformamide changes acetone into, obtains the result shown in Fig. 4,5 equally.
Embodiment 10 just changes the heavy metal ion standard solution into lead, cadmium and bismuth ion standard solution by plumbous and cadmium ion standard solution by the method for embodiment 1, obtains the result shown in Fig. 4,5 equally.
Embodiment 11 just changes the heavy metal ion standard solution into lead, cadmium and mercury ion standard solution by plumbous and cadmium ion standard solution by the method for embodiment 1, obtains the result shown in Fig. 4,5 equally.
As shown in Figure 5, cyclodextrin/Graphene modified glassy carbon electrode is to Pb
2+And Cd
2+Good stripping volt-ampere response is arranged, and along with Pb
2+And Cd
2+The increase of concentration, the response of peak current also increase gradually.The respective concentration of the intensity of peak current and metallic ion is carried out linear fit be further analyzed as can be known, 1 * 10
-10～9 * 10
-9In the M scope, peak current and Pb
2+Concentration linear, linear equation be y (
)=0.223x (nM)+0.145, its minimum detectability are 9.42 * 10
-11M.In contrast to this, 5 * 10
-10～9 * 10
-9In the M scope, peak current and Cd
2+Concentration linear, and linear equation be y (
)=0.281x (nM)-0.086, minimum detectability are 6.73 * 10
-11M.
The electrode of the present invention's preparation has good stable and reappearance, and for same modified electrode, the relative standard deviation of 10 repeated tests is 1.93%.And for 6 parallel poles that prepare simultaneously, its relative standard deviation is also within 5%.In addition, in whole test process, electrode does not need to prepare again or activate, and this electrode that proves that further we prepare has good stable and reappearance.
Claims (10)
1. the preparation method of cyclodextrin/graphene nanometer composite modified electrode comprises the steps:
A. the concentrated sulphuric acid and the 20-100 milliliter mass concentration that add 10-100 milliliter mass concentration and be 95-98% in 50-5000 milliliter round-bottomed flask are the red fuming nitric acid (RFNA) of 65-68%, stirred 5-50 minute at 0 ℃ of condition of ice bath lower magnetic force, add 2-200 gram natural flake graphite then, vigorous stirring prevents from reuniting; After waiting to be uniformly dispersed, add 10-200 gram potash chlorate, remove at last under the ice bath room temperature and reacted 20-150 hour; After question response was finished, with the product washing, ultrasonic peeling off with the NaOH flocculation and in 20-80 ℃ of dry 2-10 hour, ground, and gets the graphene oxide pressed powder;
B. graphene oxide is dissolved in the deionized water, add excessive hydroxypropyl-
-cyclodextrin, ultrasonic dispersion 10-60 minute; The auxiliary reaction down of microwave 10 minutes-2 hours, microwave power was 100-800 watt, and temperature of reaction is 20-80 ℃; Add reductive agent subsequently, centrifugal under 3000-10000 rev/min rotating speed after reaction finishes in 50-100 ℃ of down reaction 10-120 minute, and use the absolute ethyl alcohol cyclic washing, with remove unreacted hydroxypropyl-
-cyclodextrin in 30-120 ℃ of following vacuum drying 2-20 hour, namely gets product cyclodextrin/graphene nanometer composite at last;
C. cyclodextrin/graphene nanometer composite the dissolution with solvents that above-mentioned steps is made, controlling its concentration is the 0.5-50 mg/ml, add 5% the Nafion solution of cyclodextrin/graphene nanometer composite liquor capacity 0.1-10% again, ultrasonic dispersion 10-60 minute, obtain uniform dispersion liquid; Pipette the above-mentioned dispersion liquid of 3-10 microlitre with the micropipette rifle, drip and to be coated in the glass-carbon electrode surface of handling well, dry under the room temperature, obtain cyclodextrin/graphene nanometer composite modified electrode.
2. as the preparation method of the described cyclodextrin of claim 1/graphene nanometer composite modified electrode, it is characterized in that: step
In used reductive agent be in ammoniacal liquor, hydrazine hydrate, NaOH, sodium borohydride, the vitamin C one or more.
3. as the preparation method of the described cyclodextrin of claim 1/graphene nanometer composite modified electrode, it is characterized in that: step
Solvent for use is deionized water, ethanol, acetone, N, one or more in the dinethylformamide.
4. obtain cyclodextrin/graphene nanometer composite modified electrode by the described preparation method of claim 1.
5. the application of the described cyclodextrin of claim 4/graphene nanometer composite modified electrode in detecting heavy metal ion.
6. application as claimed in claim 5 is characterized in that: described detection refers to environment measuring or water analysis.
7. application as claimed in claim 5 is characterized in that:
As working electrode, saturated calomel electrode is as contrast electrode with cyclodextrin/graphene nanometer composite modified glassy carbon electrode, and platinum electrode is to electrode, constitutes three-electrode system thus; When measuring heavy metal ion, it is the buffer solution of 3.0-6.0 that three-electrode system is placed 20 milliliters 0.1 mol pH earlier, scans for several times until obtaining level and smooth curve, with the activation of the electrode surface of finishing the work with cyclic voltammetry; Then under stirring condition, in above-mentioned buffer solution, add certain density heavy metal ion solution with the micropipette rifle successively, enrichment 30-600 second under current potential-0.4～-1.8 volt, record the stripping volt-ampere curve simultaneously with the reverse scan of square wave anodic stripping voltammetry.
8. application as claimed in claim 7 is characterized in that: used buffer solution is acetic acid-sodium acetate, ammonium chloride-hydrochloric acid, a kind of in disodium-hydrogen-sodium dihydrogen phosphate buffer.
9. application as claimed in claim 7 is characterized in that: used metal ion solution is one or more in lead, cadmium, mercury, silver, chromium, copper, zinc, the bismuth solution.
10. application as claimed in claim 7 is characterized in that, the concentration of described heavy metal ion is 1 * 10
-4-1 * 10
-8Mol.
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