CN105136883A - Preparation method of silver-loaded graphene sensor used for detecting lead ions in water - Google Patents
Preparation method of silver-loaded graphene sensor used for detecting lead ions in water Download PDFInfo
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- CN105136883A CN105136883A CN201510504309.9A CN201510504309A CN105136883A CN 105136883 A CN105136883 A CN 105136883A CN 201510504309 A CN201510504309 A CN 201510504309A CN 105136883 A CN105136883 A CN 105136883A
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Abstract
The invention discloses a preparation method of a silver-loaded graphene sensor used for detecting lead ions in water. The preparation method comprises following steps: silver nitrate is added dropwise into graphene oxide so as to obtain a mixed solution; the mixed solution is subjected to water bath treatment, a NaOH solution is added dropwise, and an obtained mixture is cooled; the mixture is delivered into centrifuge tubes for centrifugation, an obtained supernatant liquid is discarded, and an obtained product is subjected to constant temperature drying so as to obtain a graphene/silver nano composite material powder; the graphene/silver nano composite material powder is uniformly mixed with graphite via ultrasonic treatment, and liquid paraffin is added so as to obtain a finished mixture; the finished mixture is subjected to compression moulding and is connected with copper wires so as to obtain a sensor; and the sensor is subjected to polishing grinding with a polishing powder, is washed, and is dried in the air so as to obtain the silver-loaded graphene sensor. According to the preparation method, graphene is loaded with silver successfully, electron mobility is increased greatly, and sensor internal resistance is reduced.
Description
Technical field
The present invention relates to electrochemical sensor field and electrochemical field, particularly a kind of preparation method of the graphene-supported silver-colored sensor for detecting lead ion in water.
Background technology
Graphene has the specific surface area (2630m of good thermal conductivity, stronger electric conductivity, high strength (110GPa) and super large
2/ g).The performance of these excellences makes Graphene have good application prospect in fields such as sensor, ultracapacitor, nano electron device, hydrogen storage material and compound substances.Graphene has high conductivity and large specific surface area, and therefore it can be used as electrode material for building capacitor and sensor.Graphene doping is one of important channel realizing graphene functionalized, and be a kind of effective means of regulation and control Graphene electricity and optical property, the Graphene after doping has huge application prospect because of it, has become the focus that researchist pays close attention to.In recent years, the functionalization of Graphene makes great progress, but in order to give full play to the excellent properties of Graphene, its application of further expansion, also need to develop and improve new functional method, the method of the group of controlling functions, site and number of functional groups etc. is set up as needed, need the functional method developing the intrinsic property that should as far as possible keep it good while functionalization, also need to remove unnecessary functional group when being based upon device application and the method etc. recovering the structure and properties of Graphene.After the row key issue such as scale preparation and effective efficiency method realizing Graphene is resolved, the range of application of Graphene will be more wide.
Plumbous (II) is a kind of common environmental pollutants, due to its non-biodegradable, bioaccumulation effect and just have the features such as larger toxicity under low concentration, one of important indicator becoming environmental monitoring.Therefore the analytical approach developing fast and convenient detection micro lead (II) is significant.At present, the analytical approach measuring micro lead mainly contains atomic absorption method, inductive coupling plasma mass spectrometry and atomic fluorescence method etc.But said method also exists, and instrument cost is high, complicated operation, sample preparation step is by the limitation such as loaded down with trivial details.
Summary of the invention:
In order to overcome the deficiency in above-mentioned prior art, the object of the present invention is to provide a kind of preparation method of the graphene-supported silver-colored sensor for detecting lead ion in water, on Graphene, load silver, improves the mobility of electronics widely, decreases the internal resistance of sensor.
To achieve these goals, technical scheme of the present invention is achieved in that
For detecting the preparation method of the graphene-supported silver-colored sensor of lead ion in water, comprise the following steps:
(1) get the nano level graphene oxide of 2mmol/L-6mmol/L of 20-30ml, drip the 10mmol/L silver nitrate ultrasonic mixing 30min of 5-7ml, obtain mixed solution;
(2) mixed liquor of step (1) is transferred in 70 DEG C of waters bath with thermostatic control, under magnetic agitation effect, drip the 4mol/LNaOH solution of 7ml ~ 10ml, reaction 5-15min, thing cooling to be mixed;
(3) pour in centrifuge tube by potpourri in step (2), centrifugal 5min under 8000 turns, observes lower leaf on mixed liquor obvious, outwell supernatant liquor, 80 DEG C of freeze-day with constant temperature, until moisture is dried completely, namely obtain Graphene/argentum nano composite material powder;
(4) by Graphene/argentum nano composite material powder of preparing and the ultrasonic mixing of graphite, porphyrize, wherein graphene-supported silver in mass ratio: graphite=1:(2.5-5), obtain the solid nanoparticles mixed;
(5) solid nanoparticles of mixing in step (4) is placed in small beaker, adds the whiteruss of the quality summation 4 times of potpourri wherein, obtain final mixture;
(6) by compressing for the final mixture obtained in step (5) and connect copper wire, sensor is obtained;
(7) sensor burnishing powder prepared by step (6) is carried out polishing grinding; After washing, use nitric acid, ethanol, water ultrasonic cleaning again; Be placed in ventilation naturally to dry for 10 ~ 15 days, obtain final graphene-supported silver-colored sensor to be prepared.
Beneficial effect of the present invention:
(1) use cheap material with carbon element to prepare electrochemical sensor, prepare material to human non-toxic, environmentally safe.
(2) adopt graphene-supported ag material, compared with the glass-carbon electrode bought, the internal resistance in certain solution reduces, and substantially increases in electrode the ability transmitting electronics, adds the sensitivity of measurement.
(3) sensor of gained of the present invention is for detecting the lead ion in solution, measures the hydrochloric acid solution that medium is the 0.1M of PH=4; Adopt differential pulse voltammetry (DPV), its location parameter is: pulse-response amplitude 0.025V, pulse width 0.01S, and scanning current potential is-0.1V ~ 0.5V; Completely the same with the volt-ampere circular chart of glass-carbon electrode in certain solution bought.
(4) sensor stability prepared is good, highly sensitive, be easy to carry, cost is low.
(5) gained sensor of the present invention is for measuring the lead ion in solution, and crest voltage is 0.081V, and the measurement range of lead ion is 1*10
-4~ 1*10
-6m/L, detectability can reach 1*10
-6m/L.
Accompanying drawing explanation
Fig. 1 is the volt-ampere circular chart of glass-carbon electrode in 0.1MKCl and 0.1M potassium ferricyanide solution.
Fig. 2 is the volt-ampere circular chart of graphene-supported silver-colored sensor in 0.1MKCl and 0.1M potassium ferricyanide solution.
Fig. 3 is the AC impedance figure of glass-carbon electrode in 0.1MKCl and 0.1M potassium ferricyanide solution.
Fig. 4 is the AC impedance figure of graphene-supported silver-colored sensor in 0.1MKCl and 0.1M potassium ferricyanide solution.
Fig. 5 is graphene-supported silver-colored sensor is the differential pulse voltammetry circular chart of finite concentration lead ion solution at 0.1MHCl and content.
Embodiment
Below in conjunction with accompanying drawing, by specific embodiment, auspicious further stating is done to the present invention.
Embodiment one
Water in following examples all adopts redistilled water, and graphene oxide used does not have particular/special requirement, and the graphene oxide of the present embodiment is self-control, and preparation method is as follows:
Under ice bath, the concentrated sulphuric acid of 20ml98wt% is added drop-wise to 0.54gKNO
3with in the potpourri of 0.60g dag, Keep agitation, adds 2.50gKMnO in 1h
4, after stirring 2h, reaction bulb is moved to room temperature, stirs 6 days to obtain dark thick liquid; In this thick liquid, the dense H of 60ml6wt% is added under stirring condition
2sO
4, stir 2h, add the H of 20g30%
2o
2, then continue to stir 2h, continue under stirring condition, in potpourri, add the potpourri (H in potpourri of 60ml sulfuric acid and hydrogen peroxide wherein
2sO
4concentration is 5wt%, H
2o
2concentration is 0.5wt%), standing sedimentation 2 days, discards upper liquid, obtains the slurry of black, washes with water to neutrality, and ultrasonic stripping 30min, obtains the yellow solution of clarification, is drying to obtain graphene oxide (GO).
The preparation method of the sensor of the present embodiment, comprises the following steps:
(1) get the nano level graphene oxide of 5mmol/L of 25ml, drip the 10mmol/L silver nitrate ultrasonic mixing 30min of 6ml, obtain mixed solution;
(2) mixed liquor of step (1) is transferred in 70 DEG C of waters bath with thermostatic control, under magnetic agitation effect, drip the 4mol/LNaOH solution of 8ml, reaction 10min, thing cooling to be mixed;
(3) pour in centrifuge tube by potpourri in step (2), centrifugal 5min under 8000 turns, observes lower leaf on mixed liquor obvious, outwell supernatant liquor, 80 DEG C of freeze-day with constant temperature, until moisture is dried completely, namely obtain Graphene/argentum nano composite material powder;
(4) by Graphene/argentum nano composite material powder of preparing and the ultrasonic mixing of graphite, porphyrize, wherein graphene-supported silver in mass ratio: graphite=1:2.5, obtains the solid nanoparticles mixed;
(5) solid nanoparticles of mixing in step (4) is placed in small beaker, adds the whiteruss of the quality summation 4 times of potpourri wherein, obtain final mixture;
(6) final mixture obtained in step (5) being filled in diameter is in the pvc pipe of 2mm, long 10mm, and the copper wire of connecting length 10mm, obtain sensor;
(7) sensor burnishing powder prepared by step (6) is carried out polishing grinding; After washing, use nitric acid, ethanol, water ultrasonic cleaning again; Be placed in ventilation naturally to dry for 15 days, obtain final graphene-supported silver-colored sensor to be prepared.
Figure 1 shows that the cyclic voltammogram of glass-carbon electrode, glass-carbon electrode is working electrode, platinum electrode is auxiliary electrode, mercurous chloride electrode does contrast electrode, and arranging interpotential interval is 5mV, and sample frequency is 100Hz, time delay 5s, initial potential-0.2V, noble potential 0.6V, sweep speed 100 (mV/s) the circulation number of turns 5 is enclosed.Solution in electrolytic cell is potassium chloride and the 0.1M potassium ferricyanide mixed solution of 0.1M.
First the process of glass-carbon electrode spreads the burnishing powder (Al of a small amount of 0.3 μm and 0.05um on polishing cloth
2o
3), then use washed with de-ionized water electrode surface, move in ultrasonic water bath and clean, each 2 ~ 3 minutes, in triplicate, finally use 1:1 ethanol, 1:1 nitric acid and distilled water ultrasonic cleaning successively.
As can be seen from Figure 1 the magnitude of voltage of glass-carbon electrode oxidation peak is 0.0214V, and current value is 5.387 × 10
-4a/cm
2.The magnitude of voltage of reduction peak is-0.405V, and electric current is-7.839 × 10
-4a/cm
2.
Figure 2 shows that the cyclic voltammogram of graphene-supported silver-colored sensor prepared by the present embodiment, wherein graphene-supported silver-colored sensor is working electrode, platinum electrode is auxiliary electrode, mercurous chloride electrode does contrast electrode, and arranging interpotential interval is 5mV, and sample frequency is 100Hz, time delay 5s, initial potential-0.2V, noble potential 0.6V, sweep speed 100 (mV/s) the circulation number of turns 5 is enclosed.Solution in electrolytic cell is potassium chloride and the 0.1M potassium ferricyanide mixed solution of 0.1M.
First the pre-service of graphene-supported silver-colored sensor spreads the burnishing powder (Al of a small amount of 0.3 μm and 0.05um on polishing cloth
2o
3), then use washed with de-ionized water electrode surface, move in ultrasonic water bath and clean, each 2 ~ 3 minutes, in triplicate, finally use 1:1 ethanol, 1:1 nitric acid and distilled water ultrasonic cleaning successively.
The magnitude of voltage of graphene-supported silver-colored sensor oxidation peak is 0.0214V, and electric current is 5.387 × 10
4a/cm
2. the magnitude of voltage of reduction peak is-0.405V, and current value is-7.839 × 10
4a/cm
2.
Contrasted from Fig. 1 and Fig. 2, the glass-carbon electrode purchased is consistent with the volt-ampere circular chart of graphene sensor, and thus graphene-supported silver-colored sensor is consistent with glass-carbon electrode chemical property.
Figure 3 shows that AC impedance (EIS) figure of glass-carbon electrode, wherein glass-carbon electrode is working electrode, platinum electrode is auxiliary electrode, mercurous chloride electrode does contrast electrode, DC potential 0V, direct current amplitude 10mV, original frequency 100000, stop frequency 0.01, time delay 5s, the solution in electrolytic cell is potassium chloride and the 0.1M potassium ferricyanide mixed solution of 0.1M.
First the process of glass-carbon electrode spreads the burnishing powder (Al of a small amount of 0.3 μm and 0.05um on polishing cloth
2o
3), then use washed with de-ionized water electrode surface, move in ultrasonic water bath and clean, each 2 ~ 3 minutes, in triplicate, finally use 1:1 ethanol, 1:1 nitric acid and distilled water ultrasonic cleaning successively.
EIS is one of effective tool exploring electrode interface character, wherein spectrogram is generally divided into HFS and low frequency part, wherein HFS is dynamics Controlling region, low frequency part is diffusion control area, Nyquist curve as shown in the figure in figure starting point A represent the impedance of measurement system electrolyte inside, B point and the ordinate difference of A point and the radius R of circular arc, under the condition that method of testing is the same, can be equal to the electrode resistance of working electrode.R (middle semicircle) is larger, illustrates that Ion transfer impedance raises; Wherein glass-carbon electrode R=405.24 ohm.
As shown in Figure 4, AC impedance (EIS) figure of the graphene-supported silver-colored sensor prepared by the present embodiment, graphene-supported silver-colored sensor is working electrode, and platinum electrode is auxiliary electrode, and mercurous chloride electrode does contrast electrode, DC potential 0V, direct current amplitude 10mV, original frequency 100000, stops frequency 0.01, time delay 5s, the solution in electrolytic cell is potassium chloride and the 0.1M potassium ferricyanide mixed solution of 0.1M.
First the pre-service of graphene-supported silver-colored sensor spreads the burnishing powder (Al of a small amount of 0.3 μm and 0.05um on polishing cloth
2o
3), then use washed with de-ionized water electrode surface, move in ultrasonic water bath and clean, each 2 ~ 3 minutes, in triplicate, finally use 1:1 ethanol, 1:1 nitric acid and distilled water ultrasonic cleaning successively.
EIS is one of effective tool exploring electrode interface character, wherein spectrogram is generally divided into HFS and low frequency part, wherein HFS is dynamics Controlling region, low frequency part is diffusion control area, Nyquist curve as shown in the figure in figure starting point A represent the impedance of measurement system electrolyte inside, B point and the ordinate difference of A point and the radius R of circular arc, under the condition that method of testing is the same, can be equal to the electrode resistance of working electrode.R (middle semicircle) is larger, illustrates that Ion transfer impedance raises; As shown in Figure 4, the R of graphene-supported silver-colored sensor
1=18.101 ohm " R=405.24 ohm, so the graphene-supported silver electrode of R glass-carbon electrode; Can find out that the slope of straight line is directly proportional to the diffusion impedance of solution by tan θ=ω RC by experimental principle formula, that is upper figure cathetus CD, C
1d
1slope and the diffusion resistance of solution be directly proportional, glass-carbon electrode tanB=2.47 in experiment, and graphene-supported silver-colored sensor tanB1=1.51, than glass carbon, wherein glass-carbon electrode is high a lot of as the rate of working electrode electron transfer in the solution for graphene-supported silver-colored sensor.
By the AC impedance of the glass-carbon electrode of Fig. 3, Fig. 4, more known with the internal resistance of the sensor of the present embodiment, the internal resistance of the present embodiment sensor is little, is derived as 18.101 ohm from figure.
The sensing range of the sensor measurement lead ion of gained, detectability as shown in Figure 5, the differential pulse figure of lead ion in graphene-supported silver-colored sensor measurement water.Differential Pulse Stripping Voltammetry is a kind of new electrochemical analysis method grown up by stripping voltammetry, because it has very high letter valency ratio, is one of modern most important electrochemical analysis method.It is the method for the sensitiveest detectable concentration, is widely used in the analytical work of trace materials, usually much sensitive than molecule or atomic absorption spectrum, most of chromatographic process.The heavy metal sensitivity such as lead are only second to the neutron activation method in radiochemical analysis, and reliably, fast and convenient, analysis cost is low, sample does not need digestion or only needs simple digestion just can measure.Differential Pulse Stripping Voltammetry is except sensitivity for analysis height, and it also has the features such as analysis speed is fast, mensuration element is many, analytical sample is few, instrument is simply inexpensive.
Graphene-supported silver-colored sensor is working electrode, platinum electrode is auxiliary electrode, mercurous chloride electrode does contrast electrode, wherein initial potential and electro-deposition current potential are 0.5V, stopping current potential is-0.1V, and current potential increment is 0.004V, and pulse height is 0.025V, pulse width is 0.01s, and sampling width is 0.005s.Be 0.1MHCl standard solution and certain density lead ion mixed liquor in electrolytic cell.
First the pre-service of graphene-supported silver-colored sensor spreads the burnishing powder (Al of a small amount of 0.3 μm and 0.05um on polishing cloth
2o
3), then use washed with de-ionized water electrode surface, move in ultrasonic water bath and clean, each 2 ~ 3 minutes, in triplicate, finally use 1:1 ethanol, 1:1 nitric acid and distilled water ultrasonic cleaning successively.As shown in Figure 5, be E=0.081V place at voltage, the electric current in the concentration of lead ion and solution, at 1*10
-4~ 1*10
-6there is certain corresponding relation within the scope of M/L, it detects spacing 1*10
-6m/L.Along with plumbum ion concentration reduces, in solution, plumbum ion concentration and peak current have certain correlativity.
Embodiment two
The preparation method of the sensor of the present embodiment, comprises the following steps:
(1) get the nano level graphene oxide of 2mmol/L of 21ml, drip the 10mmol/L silver nitrate ultrasonic mixing 30min of 5ml, obtain mixed solution;
(2) mixed liquor of step (1) is transferred in 70 DEG C of waters bath with thermostatic control, under magnetic agitation effect, drip the 4mol/LNaOH solution of 7ml, reaction 10min, thing cooling to be mixed;
(3) pour in centrifuge tube by potpourri in step (2), centrifugal 5min under 8000 turns, observes lower leaf on mixed liquor obvious, outwell supernatant liquor, 80 DEG C of freeze-day with constant temperature, until moisture is dried completely, namely obtain Graphene/argentum nano composite material powder;
(4) by Graphene/argentum nano composite material powder of preparing and the ultrasonic mixing of graphite, porphyrize, wherein graphene-supported silver in mass ratio: graphite=1:2.5, obtains the solid nanoparticles mixed;
(5) solid nanoparticles of mixing in step (4) is placed in small beaker, adds the whiteruss of the quality summation 4 times of potpourri wherein, obtain final mixture;
(6) final mixture obtained in step (5) being filled in diameter is in the pvc pipe of 2mm, long 10mm, and the copper wire of connecting length 10mm, obtain sensor;
(7) sensor burnishing powder prepared by step (6) is carried out polishing grinding; After washing, use nitric acid, ethanol, water ultrasonic cleaning again; Be placed in ventilation naturally to dry for 10 ~ 15 days, obtain final graphene-supported silver-colored sensor to be prepared,
The sensor volt-ampere circulation of the present embodiment, close with embodiment one, consistent with glass-carbon electrode volt-ampere circular chart.The internal resistance of the sensor measured in the AC impedance of sensor is within the scope of 15 ~ 20 ohm; Differential pulse figure in lead ion solution and detectable concentration scope shown in embodiment one, detectability are consistent.
Embodiment three
The preparation method of the sensor of the present embodiment, comprises the following steps:
(1) get the nano level graphene oxide of 3mmol/L of 23ml, drip the 10mmol/L silver nitrate ultrasonic mixing 30min of 5ml, obtain mixed solution;
(2) mixed liquor of step (1) is transferred in 70 DEG C of waters bath with thermostatic control, under magnetic agitation effect, drip the 4mol/LNaOH solution of 7ml, reaction 10min, thing cooling to be mixed;
(3) pour in centrifuge tube by potpourri in step (2), centrifugal 5min under 8000 turns, observes lower leaf on mixed liquor obvious, outwell supernatant liquor, 80 DEG C of freeze-day with constant temperature, until moisture is dried completely, namely obtain Graphene/argentum nano composite material powder;
(4) by Graphene/argentum nano composite material powder of preparing and the ultrasonic mixing of graphite, porphyrize, wherein graphene-supported silver in mass ratio: graphite=1:2.5, obtains the solid nanoparticles mixed;
(5) solid nanoparticles of mixing in step (4) is placed in small beaker, adds the whiteruss of the quality summation 4 times of potpourri wherein, obtain final mixture;
(6) final mixture obtained in step (5) being filled in diameter is in the pvc pipe of 2mm, long 10mm, and the copper wire of connecting length 10mm, obtain sensor;
(7) sensor burnishing powder prepared by step (6) is carried out polishing grinding; After washing, use nitric acid, ethanol, water ultrasonic cleaning again; Be placed in ventilation naturally to dry for 10 ~ 15 days, obtain final graphene-supported silver-colored sensor to be prepared.
The sensor volt-ampere circulation of the present embodiment, close with embodiment one, consistent with glass-carbon electrode volt-ampere circular chart.The internal resistance of the sensor measured in the AC impedance of sensor is within the scope of 15 ~ 20 ohm; Differential pulse figure in lead ion solution and detectable concentration scope shown in embodiment one, detectability are consistent.
Embodiment four
The preparation method of the sensor of the present embodiment, comprises the following steps:
(1) get the nano level graphene oxide of 6mmol/L of 28ml, drip the 10mmol/L silver nitrate ultrasonic mixing 30min of 6ml, obtain mixed solution;
(2) mixed liquor of step (1) is transferred in 70 DEG C of waters bath with thermostatic control, under magnetic agitation effect, drip the 4mol/LNaOH solution of 9ml, reaction 10min, thing cooling to be mixed;
(3) pour in centrifuge tube by potpourri in step (2), centrifugal 5min under 8000 turns, observes lower leaf on mixed liquor obvious, outwell supernatant liquor, 80 DEG C of freeze-day with constant temperature, until moisture is dried completely, namely obtain Graphene/argentum nano composite material powder;
(4) by Graphene/argentum nano composite material powder of preparing and the ultrasonic mixing of graphite, porphyrize, wherein graphene-supported silver in mass ratio: graphite=1:2.5, obtains the solid nanoparticles mixed;
(5) solid nanoparticles of mixing in step (4) is placed in small beaker, adds the whiteruss of the quality summation 4 times of potpourri wherein, obtain final mixture;
(6) final mixture obtained in step (5) being filled in diameter is in the pvc pipe of 2mm, long 10mm, and the copper wire of connecting length 10mm, obtain sensor;
(7) sensor burnishing powder prepared by step (6) is carried out polishing grinding; After washing, use nitric acid, ethanol, water ultrasonic cleaning again; Be placed in ventilation naturally to dry for 10 ~ 15 days, obtain final graphene-supported silver-colored sensor to be prepared.
The sensor volt-ampere circulation of the present embodiment, close with embodiment one, consistent with glass-carbon electrode volt-ampere circular chart.The internal resistance of the sensor measured in the AC impedance of sensor is within the scope of 15 ~ 20 ohm; Differential pulse figure in lead ion solution and detectable concentration scope shown in embodiment one, detectability are consistent.
Embodiment five
The preparation method of the sensor of the present embodiment, comprises the following steps:
(1) get the nano level graphene oxide of 6mmol/L of 30ml, drip the 10mmol/L silver nitrate ultrasonic mixing 30min of 7ml, obtain mixed solution;
(2) mixed liquor of step (1) is transferred in 70 DEG C of waters bath with thermostatic control, under magnetic agitation effect, drip the 4mol/LNaOH solution of 10ml, reaction 10min, thing cooling to be mixed;
(3) pour in centrifuge tube by potpourri in step (2), centrifugal 5min under 8000 turns, observes lower leaf on mixed liquor obvious, outwell supernatant liquor, 80 DEG C of freeze-day with constant temperature, until moisture is dried completely, namely obtain Graphene/argentum nano composite material powder;
(4) by Graphene/argentum nano composite material powder of preparing and the ultrasonic mixing of graphite, porphyrize, wherein graphene-supported silver in mass ratio: graphite=1:2.5, obtains the solid nanoparticles mixed;
(5) solid nanoparticles of mixing in step (4) is placed in small beaker, adds the whiteruss of the quality summation 4 times of potpourri wherein, obtain final mixture;
(6) final mixture obtained in step (5) being filled in diameter is in the pvc pipe of 2mm, long 10mm, and the copper wire of connecting length 10mm, obtain sensor;
(7) sensor burnishing powder prepared by step (6) is carried out polishing grinding; After washing, use nitric acid, ethanol, water ultrasonic cleaning again; Be placed in ventilation naturally to dry for 10 ~ 15 days, obtain final graphene-supported silver-colored sensor to be prepared.
The sensor volt-ampere circulation of the present embodiment, close with embodiment one, consistent with glass-carbon electrode volt-ampere circular chart.The internal resistance of the sensor measured in the AC impedance of sensor is within the scope of 15 ~ 20 ohm; Shown in differential pulse figure in lead ion solution and embodiment one, concentration range, detectability are consistent.
Claims (2)
1., for detecting the preparation method of the graphene-supported silver-colored sensor of lead ion in water, it is characterized in that, comprise the following steps:
(1) get the nano level graphene oxide of 2mmol/L-6mmol/L of 20-30ml, drip the 10mmol/L silver nitrate ultrasonic mixing 30min of 5-7ml, obtain mixed solution;
(2) mixed liquor of step (1) is transferred in 70 DEG C of waters bath with thermostatic control, under magnetic agitation effect, drip the 4mol/LNaOH solution of 7ml ~ 10ml, reaction 5-15min, thing cooling to be mixed;
(3) pour in centrifuge tube by potpourri in step (2), centrifugal 5min under 8000 turns, observes lower leaf on mixed liquor obvious, outwell supernatant liquor, 80 DEG C of freeze-day with constant temperature, until moisture is dried completely, namely obtain Graphene/argentum nano composite material powder;
(4) by Graphene/argentum nano composite material powder of preparing and the ultrasonic mixing of graphite, porphyrize, wherein graphene-supported silver in mass ratio: graphite=1:(2.5-5), obtain the solid nanoparticles mixed;
(5) solid nanoparticles of mixing in step (4) is placed in small beaker, adds the whiteruss of the quality summation 4 times of potpourri wherein, obtain final mixture;
(6) final mixture that obtains in step (5) is the compressing and copper wire connected, obtains sensor;
(7) sensor burnishing powder prepared by step (6) is carried out polishing grinding; After washing, use nitric acid, ethanol, water ultrasonic cleaning again; Be placed in ventilation naturally to dry for 10 ~ 15 days, obtain final graphene-supported silver-colored sensor to be prepared.
2. the preparation method of the graphene-supported silver-colored sensor for detecting lead ion in water according to claim 1, is characterized in that, comprise the following steps:
(1) get the nano level graphene oxide of 5mmol/L of 25ml, drip the 10mmol/L silver nitrate ultrasonic mixing 30min of 6ml, obtain mixed solution;
(2) mixed liquor of step (1) is transferred in 70 DEG C of waters bath with thermostatic control, under magnetic agitation effect, drip the 4mol/LNaOH solution of 8ml, reaction 10min, thing cooling to be mixed;
(3) pour in centrifuge tube by potpourri in step (2), centrifugal 5min under 8000 turns, observes lower leaf on mixed liquor obvious, outwell supernatant liquor, 80 DEG C of freeze-day with constant temperature, until moisture is dried completely, namely obtain Graphene/argentum nano composite material powder;
(4) by Graphene/argentum nano composite material powder of preparing and the ultrasonic mixing of graphite, porphyrize, wherein graphene-supported silver in mass ratio: graphite=1:2.5, obtains the solid nanoparticles mixed;
(5) solid nanoparticles of mixing in step (4) is placed in small beaker, adds the whiteruss of the quality summation 4 times of potpourri wherein, obtain final mixture;
(6) final mixture obtained in step (5) being filled in diameter is in the pvc pipe of 2mm, long 10mm, and the copper wire of connecting length 10mm, obtain sensor;
(7) sensor burnishing powder prepared by step (6) is carried out polishing grinding; After washing, use nitric acid, ethanol, water ultrasonic cleaning again; Be placed in ventilation naturally to dry for 15 days, obtain final graphene-supported silver-colored sensor to be prepared.
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| CN107413294A (en) * | 2017-05-19 | 2017-12-01 | 西安石油大学 | A kind of method that graphene-supported silver handles high Oil repellent domestic water |
| CN107412882A (en) * | 2017-08-01 | 2017-12-01 | 浙江理工大学 | A kind of preparation method for attaching flexible artificial skin receptor |
| CN107991372A (en) * | 2017-11-22 | 2018-05-04 | 大连大学 | A kind of method for lead ion detection |
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| CN106582857A (en) * | 2016-12-16 | 2017-04-26 | 昆明理工大学 | Preparation method of metal organic framework for loading nano silver |
| CN107413294A (en) * | 2017-05-19 | 2017-12-01 | 西安石油大学 | A kind of method that graphene-supported silver handles high Oil repellent domestic water |
| CN107287884A (en) * | 2017-08-01 | 2017-10-24 | 浙江理工大学 | A kind of preparation method for attaching ventilative artificial skin receptor |
| CN107412882A (en) * | 2017-08-01 | 2017-12-01 | 浙江理工大学 | A kind of preparation method for attaching flexible artificial skin receptor |
| CN107287884B (en) * | 2017-08-01 | 2019-05-31 | 浙江理工大学 | A kind of preparation method attaching ventilative artificial skin receptor |
| CN107412882B (en) * | 2017-08-01 | 2020-04-07 | 浙江理工大学 | Preparation method of attached flexible artificial skin receptor |
| CN107991372A (en) * | 2017-11-22 | 2018-05-04 | 大连大学 | A kind of method for lead ion detection |
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