CN103235019B - 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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- CN103235019B CN103235019B CN201310128568.7A CN201310128568A CN103235019B CN 103235019 B CN103235019 B CN 103235019B CN 201310128568 A CN201310128568 A CN 201310128568A CN 103235019 B CN103235019 B CN 103235019B
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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, be specifically related to a kind of preparation method of cyclodextrin/graphene nanometer composite modified glassy carbon electrode and for detection of 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 for a long time in environment, also can be by food chain enrichment in people and animal and plant body.In recent years, heavy metal pollution, because the threat that it causes environment and human health is on the rise, has caused great attention 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.Advantages such as compared with classic method, electrochemical methods is easy because of it, fast, sensitive, accurate and obtained application widely.The anodic stripping voltammetry (Anodic Stripping Voltammetry ASV) the present invention is based in electrochemical methods detects.It mainly comprises deposition and two processes of stripping, that is: first, detected ion is deposited to the surface of reduction at working electrode under certain potentials.Then, when reverse scan electrode potential, the material generation oxidation reaction having deposited and Stripping Voltammetry 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
2hydridization carbon atom is piled up the new carbon of the bi-dimensional cellular shape crystalline network forming, and its thickness is only 0.35nm, is the thinnest in the world two-dimensional material.To have specific surface area large 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, the 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 impact of reuniting, and has also increased its selection and adsorptive power to heavy metal ion simultaneously.Using this nano-complex as inductive material, invent a kind of detection fast, highly sensitive, when favorable reproducibility, detect the method for trace heavy metal ion, and the method is nontoxic to environment and human health.
summary of the invention:
The object of the present invention is to provide a kind of method 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 using this electrode as working electrode, adopt the saturated calomel electrode of buying is contrast electrode simultaneously, platinum electrode is to electrode, completes the trace detection to heavy metal ion by the three-electrode system forming.In testing process, adopt square wave anodic stripping voltammetry.
The preparation method of a kind of cyclodextrin/graphene nanometer composite of the present invention modified glassy carbon electrode, comprises the steps:
1. the pre-service of glass-carbon electrode: by glass-carbon electrode (3 millimeters of diameters) on polishing cloth with the Al of 0.05 micron
2o
3powder is polished to minute surface.First ultrasonic cleaning 2 minutes in ultrapure water after polishing, then use successively absolute ethyl alcohol, ultrapure water ultrasonic cleaning 5 minutes, finally dry up with nitrogen, stand-by.
2. the preparation of cyclodextrin/graphene nanometer composite modified glassy carbon electrode:
First, utilize improved Hummers method to prepare graphene oxide by oxidation, mechanical stripping, the flocculation drying and other steps of graphite.Concrete operation step is as follows: in 50-5000 milliliter round-bottomed flask, adding 10-100 milliliter mass concentration is the red fuming nitric acid (RFNA) that the 95-98% concentrated sulphuric acid and 20-100 milliliter mass concentration are 65-68%, stir 5-50 minute at 0 DEG C of condition of ice bath lower magnetic force, then add 2-200 gram of natural flake graphite, vigorous stirring prevents from reuniting, after being uniformly dispersed, add 10-100 gram of potash chlorate, finally remove under ice bath room temperature and react 20-150 hour, after question response completes, product is washed, ultrasonic peeling off, with NaOH flocculation and in 20-80 DEG C of dry 2-10 hour, grind, obtain graphene oxide pressed powder.
Graphene oxide is dissolved in deionized water, add excessive hydroxypropyl-
-cyclodextrin, ultrasonic dispersion 10-60 minute, the auxiliary lower reaction of microwave 10 minutes-2 hours, microwave power was 100-800 watt, and temperature of reaction is 20-80 DEG C, add subsequently reductive agent, at 50-100 DEG C, react 10-120 minute, after completion of the reaction, centrifugal under the rotating speed of 3000-10000 rev/min, and use absolute ethyl alcohol cyclic washing, with remove unreacted hydroxypropyl-
-cyclodextrin, finally vacuum drying 2-20 hour at 30-120 DEG C, obtains product cyclodextrin/graphene nanometer composite.
Cyclodextrin/graphene nanometer composite dissolution with solvents that above-mentioned steps is made, controlling its concentration is 0.5-50 mg/ml, 5% the Nafion that adds again cyclodextrin/graphene nanometer composite liquor capacity 0.1-10%, ultrasonic dispersion 10-60 minute, obtains uniform dispersion liquid.Pipette the above-mentioned dispersion liquid of 3-10 microlitre with micropipette rifle, drip and be coated in the glass-carbon electrode surface of handling well, dry under room temperature, obtain the electrode that cyclodextrin/graphene nanometer composite is modified.In order to contrast, to use the same method and prepare graphene modified glass-carbon electrode and cyclodextrin modified glass-carbon electrode.
The present invention also provides a kind of method that detects trace heavy metal ion, is applicable to the trace detection of heavy metal ion in environment measuring and water analysis.Its concrete assay method is as follows: using cyclodextrin/graphene nanometer composite modified electrode of above-mentioned preparation as working electrode, saturated calomel electrode is to electrode as contrast electrode, platinum electrode, forms thus three-electrode system.Measure when heavy metal ion, three-electrode system be first placed in to the buffer solution that the 0.1 mol/L pH of 20 milliliters is 3.0-6.0, with cyclic voltammetry scanning for several times until obtain level and smooth curve, with the activation of the electrode surface of finishing the work.Then under stirring condition, in above-mentioned buffer solution, add certain density heavy metal ion solution successively with micropipette rifle, enrichment 30-600 second under current potential-0.4～-1.8 volt, then use the reverse scan of square wave anodic stripping voltammetry, record Stripping Voltammetry curve simultaneously.
The present invention's reductive agent used is one or more in ammoniacal liquor, hydrazine hydrate, NaOH, sodium borohydride and vitamin C.
Solvent for use of the present invention is one or more in deionized water, ethanol, acetone, DMF.
The present invention's buffer solution used is the one in acetic acid-sodium acetate, ammonium chloride-hydrochloric acid, disodium-hydrogen-sodium dihydrogen phosphate buffer.
The present invention's heavy metal ion solution used is one or more in lead, cadmium, mercury, silver, chromium, copper, zinc, 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 excellent electric conductivity of host-guest recognition capability, enrichment performance and the Graphene of cyclodextrin, large specific surface area simultaneously.The modification of water soluble Beta-cyclodextrin molecule has not only overcome the reunion of Graphene, is more conducive to the selectivity of heavy metal ion to catch.
In addition, the present invention is by Electrochemical Stripping voltammetry, the glass-carbon electrode of modifying taking cyclodextrin/graphene nanometer composite detects trace heavy metal ion as working electrode simultaneously, operating process is simple, quick, detection method reappearance, good stability, and greatly improved the sensitivity detecting.The modification of cyclodextrin, has the detection limit of good detection effect, especially lead ion and cadmium ion to reach respectively 9.42 × 10 to heavy metal ion
-11mol/L and 6.73 × 10
-11mol/L.
brief description of the drawings:
Interaction schematic diagram between the composition principle of Fig. 1 cyclodextrin/graphene nanometer composite and this compound and 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/L) 0.1 mol/L pH 4.5 NaAc_HAc buffer solutions in, naked glass-carbon electrode, graphene modified glass-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:
Below by the drawings and specific embodiments, the present invention is described in further detail.
embodiment 1the first step, the i.e. preparation of cyclodextrin/graphene nanometer composite modified glassy carbon electrode.
(1) pre-service of glass-carbon electrode: by glass-carbon electrode (3 millimeters of diameters) on polishing cloth with the Al of 0.05 micron
2o
3powder is polished to minute surface.After polishing first in ultrapure water ultrasonic 2 minutes, then use successively absolute ethyl alcohol, ultrapure water ultrasonic cleaning 5 minutes, finally dry up with nitrogen, stand-by.
(2) preparation of cyclodextrin/graphene nanometer composite modified glassy carbon electrode:
First, utilize improved Hummers method to prepare graphene oxide by oxidation, mechanical stripping, the flocculation drying and other steps of graphite.Concrete operation step is as follows: in 500 milliliters of round-bottomed flasks, add the concentrated sulphuric acid and 36 milliliters of red fuming nitric acid (RFNA)s that mass concentration is 65-68% that 72 milliliters of mass concentrations are 95-98%, stir 15 minutes at 0 DEG C of condition of ice bath lower magnetic force, then add 4 grams of natural flake graphites, vigorous stirring prevents from reuniting, after being uniformly dispersed, add 44 grams of potash chlorate, finally remove under ice bath room temperature and react 96 hours.After question response completes, by product washing, ultrasonic peeling off, obtains graphene oxide pressed powder for dry 6 hours with NaOH flocculation and in 40 DEG C.
Take 40 milligrams of graphene oxides and be dissolved in 80 ml deionized water, then add 1.0 grams of hydroxypropyls-
-cyclodextrin, ultrasonic dispersion 20 minutes; The auxiliary lower reaction of microwave 30 minutes, microwave power was 450 watts, and temperature of reaction is 50 DEG C; Add subsequently 500 microlitre ammoniacal liquor and 100 microlitre hydrazine hydrates, at 75 DEG C, react 30 minutes, after completion of the reaction, potpourri is poured in centrifuge tube, under the rotating speed of 8000 revs/min centrifugal 15 minutes, and with a large amount of absolute ethyl alcohol cyclic washings, with remove unreacted hydroxypropyl-
-cyclodextrin, finally vacuum drying 6 hours at 70 DEG C, obtains product cyclodextrin/graphene nanometer composite.Its preparation principle is shown in Fig. 1, and pattern and thermal stability are shown in respectively Fig. 2 and Fig. 3.
1 milliliter of DMF of 1 milligram of use of cyclodextrin/graphene nanometer composite that above-mentioned steps is made dissolves, then adds the Nafion of 20 microlitres 5%, and ultrasonic dispersion obtains uniform dispersion liquid.Pipette the above-mentioned dispersion liquid of 5 microlitre with micropipette rifle, drip and be coated in the glass-carbon electrode surface of handling well, dry under room temperature, obtain the electrode that cyclodextrin/graphene nanometer composite is modified.In order to contrast, to use the same method and prepare graphene modified glass-carbon electrode and cyclodextrin modified glass-carbon electrode.As shown in Figure 4, the performance of cyclodextrin/graphene nanometer composite modified glassy carbon electrode is better than other electrode far away.
Second step. be the detection of cyclodextrin/graphene nanometer composite modified glassy carbon electrode for heavy metal ion.Using cyclodextrin/graphene nanometer composite modified glassy carbon electrode of above-mentioned preparation as working electrode, saturated calomel electrode is to electrode as contrast electrode, platinum electrode, forms thus three-electrode system.While measuring heavy metal ion, three-electrode system is first placed in to the NaAc_HAc buffer solution that 20 milliliter of 0.1 mol/L pH is 4.5, by cyclic voltammetry with the velocity sweeping of 300 millivolts/second for several times until obtain level and smooth curve, with the activation of the electrode surface of finishing the work.Then under the condition stirring, with micropipette rifle to the lead and the cadmium standard solution that add successively a certain amount of variable concentrations in above-mentioned solution, then enrichment 120 seconds under current potential-1.2 volt is recorded Stripping Voltammetry curve with the reverse scan of square wave anodic stripping voltammetry simultaneously.
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 equally result as shown in Figure 2,3.
Embodiment 3 presses the preparation method of embodiment 1, just makes described reductive agent into sodium borohydride by ammoniacal liquor and hydrazine hydrate, obtains equally result as shown in Figure 2,3.
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 equally result as shown in Figure 2,3.
Embodiment 5 presses the preparation method of embodiment 1, just changes described reductive agent into vitamin C by ammoniacal liquor and hydrazine hydrate, obtains equally result as shown in Figure 2,3.
Embodiment 6 presses the method for embodiment 1, just changes described solvent into ethanol by DMF, obtains equally result as shown in Figure 4,5.
Embodiment 7 presses the method for embodiment 1, just changes described solvent into acetone by DMF, obtains equally result as shown in Figure 4,5.
Embodiment 8 presses the method for embodiment 1, just changes described buffer solution into ammonium chloride-hydrochloric acid buffer solution by NaAc_HAc buffer solution, obtains equally result as shown in Figure 4,5.
Embodiment 9 just changes described buffer solution into disodium-hydrogen-sodium dihydrogen phosphate buffer by NaAc_HAc buffer solution by the method for embodiment 1.Obtain equally result as shown in Figure 4,5.
Embodiment 10 just changes 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 equally result as shown in Figure 4,5.
Embodiment 11 just changes 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 equally result as shown in Figure 4,5.
As shown in Figure 5, cyclodextrin/graphene modified glass-carbon electrode is to Pb
2+and Cd
2+there is good Stripping Voltammetry response, and along with Pb
2+and Cd
2+the increase of concentration, the response of peak current also increases gradually.By the respective concentration of the intensity of peak current and metallic ion carry out Linear Quasi incompatible be further analyzed known, 1 × 10
-10～9 × 10
-9within the scope of M, peak current and Pb
2+concentration linear, linear equation be y (
)=0.223x (nM)+0.145, its minimum detectability is 9.42 × 10
-11m.In contrast to this, 5 × 10
-10～9 × 10
-9within the scope of M, peak current and Cd
2+concentration linear, and linear equation be y (
)=0.281x (nM)-0.086, minimum detectability is 6.73 × 10
-11m.
Electrode prepared by the present invention has good stability and reappearance, and for same modified electrode, the relative standard deviation of 10 repeated tests is 1.93%.And for 6 parallel poles preparing simultaneously, its relative standard deviation is also within 5%.In addition, in whole test process, electrode does not need again prepare or activate, and this electrode that further proves that we prepare has good stability and reappearance.
Claims (2)
1. cyclodextrin/graphene nanometer composite modified electrode is in the application detecting in heavy metal ion, and described cyclodextrin/graphene nanometer composite modified electrode is made by the preparation method who comprises the steps:
the pre-service of glass-carbon electrode: by glass-carbon electrode on polishing cloth with the Al of 0.05 micron
2o
3powder is polished to minute surface; After polishing first in ultrapure water ultrasonic 2 minutes, then use successively absolute ethyl alcohol, ultrapure water ultrasonic cleaning 5 minutes, finally dry up with nitrogen, stand-by;
the preparation of cyclodextrin/graphene nanometer composite modified electrode:
A. in 50-5000 milliliter round-bottomed flask, add the red fuming nitric acid (RFNA) that the concentrated sulphuric acid that 10-100 milliliter mass concentration is 95-98% and 20-100 milliliter mass concentration are 65-68%, stir 5-50 minute at 0 DEG C of condition of ice bath lower magnetic force, then add 2-200 gram of natural flake graphite, vigorous stirring prevents from reuniting; After being uniformly dispersed, add 10-200 gram of potash chlorate, finally remove under ice bath room temperature and react 20-150 hour; After question response completes, by product washing, ultrasonic peeling off, with NaOH flocculation and in 20-80 DEG C of dry 2-10 hour, grinds, and obtains graphene oxide pressed powder;
B. graphene oxide is dissolved in deionized water, add excessive hydroxypropyl-
-cyclodextrin, ultrasonic dispersion 10-60 minute; The auxiliary lower reaction of microwave 10 minutes-2 hours, microwave power was 100-800 watt, and temperature of reaction is 20-80 DEG C; Add subsequently reductive agent, at 50-100 DEG C, react 10-120 minute, after completion of the reaction, centrifugal under the rotating speed of 3000-10000 rev/min, and use absolute ethyl alcohol cyclic washing, with remove unreacted hydroxypropyl-
-cyclodextrin, finally vacuum drying 2-20 hour at 30-120 DEG C, obtains product cyclodextrin/graphene nanometer composite;
C. cyclodextrin/graphene nanometer composite dissolution with solvents above-mentioned steps being made, controlling its concentration is 0.5-50 mg/ml, 5% the Nafion solution that adds again cyclodextrin/graphene nanometer composite liquor capacity 0.1-10%, ultrasonic dispersion 10-60 minute, obtains uniform dispersion liquid; Pipette the above-mentioned dispersion liquid of 3-10 microlitre with micropipette rifle, drip and be coated in the glass-carbon electrode surface of handling well, dry under room temperature, obtain cyclodextrin/graphene nanometer composite modified electrode.
2. the application as described in claim 1, is characterized in that: step
in reductive agent used be one or more in ammoniacal liquor, hydrazine hydrate, NaOH, sodium borohydride, vitamin C.
3. the application as described in claim 1, is characterized in that: step
solvent for use is one or more in deionized water, ethanol, acetone, DMF.
4. application as claimed in claim 1, is characterized in that: described detection refers to environment measuring or water analysis.
5. application as claimed in claim 1, is characterized in that: using cyclodextrin/graphene nanometer composite modified glassy carbon electrode as working electrode, saturated calomel electrode is as contrast electrode, and platinum electrode is to electrode, forms thus three-electrode system; Measure when heavy metal ion, three-electrode system be first placed in to the buffer solution that the 0.1 mol/L pH of 20 milliliters is 3.0-6.0, with cyclic voltammetry scanning for several times until obtain level and smooth curve, with the activation of the electrode surface of finishing the work; Then under stirring condition, in above-mentioned buffer solution, add successively certain density heavy metal ion solution with micropipette rifle, enrichment 30-600 second under current potential-0.4～-1.8 volt, record Stripping Voltammetry curve with the reverse scan of square wave anodic stripping voltammetry simultaneously.
6. application as claimed in claim 5, is characterized in that: buffer solution used is acetic acid-sodium acetate, ammonium chloride-hydrochloric acid, the one in disodium-hydrogen-sodium dihydrogen phosphate buffer.
7. application as claimed in claim 5, is characterized in that: metal ion solution used is one or more in lead, cadmium, mercury, silver, chromium, copper, zinc, bismuth solution.
8. application as claimed in claim 5, is characterized in that, the concentration of described heavy metal ion is 1 × 10
-4-1 × 10
-8mol/L.
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