CN107643332B - A kind of gold combination electrode and its preparation method and application - Google Patents
A kind of gold combination electrode and its preparation method and application Download PDFInfo
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- CN107643332B CN107643332B CN201710997487.9A CN201710997487A CN107643332B CN 107643332 B CN107643332 B CN 107643332B CN 201710997487 A CN201710997487 A CN 201710997487A CN 107643332 B CN107643332 B CN 107643332B
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Abstract
The present invention provides a kind of golden combination electrodes, and included in the enhanced sensitivity layer and zirconium oxide layer of the setting of gold electrode surfaces stacked above one another, the enhanced sensitivity layer includes the compound and redox graphene of molybdenum disulfide and elemental gold；The redox graphene is capable of increasing the specific surface area of electrode, promotes selective absorption of the zirconium oxide to fenifrothion, the sulphur on molybdenum disulfide surface can be with metallographic interaction, the common electric conductivity for improving electrode material.The golden combination electrode that the present invention obtains can successfully adsorb fenifrothion, and the setting of enhanced sensitivity layer can enhance the detection sensitivity to fenifrothion；Meanwhile, it is capable to the fenifrothion of absorption be removed by electrochemical method, realize the recycling of golden combination electrode；Furthermore the gold combination electrode is higher than other similar structural compounds to the selective absorption effect of fenifrothion from far away, shows splendid selectivity.The present invention also provides the preparation methods of the golden combination electrode, and this method is easy to operate, easy to implement.
Description
Technical field
The present invention relates to technical field of electrochemical detection more particularly to a kind of golden combination electrode and preparation method thereof and in agriculture
Medicine remains the application in rapid detection technical field.
Background technique
Fenifrothion belongs to organophosphorus insecticides, can inhibit the activity of nervous system acetylcholinesterase, be widely used
In the control of insect of fruits and vegetables crops.The frequent use of fenifrothion insecticide can remain on crops, while will lead to soil
Earth pollution and water pollution are very big to human health risk.
Currently, for fenifrothion detection method there are many kinds of, such as high performance liquid chromatography, gas-chromatography, mass spectral analysis
With immunoassay etc., have many advantages, such as that accuracy is high, qualitative and quantitative analysis performance is splendid.However, these detection methods generally need
To use that expensive instrument, detection process is cumbersome, needs professional's operation, unsuitable on-site test.Therefore, one kind is needed
Simple and the quick detection fenifrothion of par sensing equipment.
Electrochemical sensor as a kind of simply sensor for easily preparing, have sample pre-treatments are easy, analysis cost is low,
Response time is short, is suitble to the advantages that on-site test, it has also become a kind of analysis method of energy fast detecting pesticide residue.This field skill
Known to art personnel, conventional electrodes used by electrochemical sensor are mostly plane electrode, and specific surface area is limited, need to modify
Nano material increase specific surface area, and most of nano material (such as common nanotube, graphene, class graphene, metal are received
Rice material etc.) detection substrate non-selectivity is adsorbed, greatly reduce the analytical effect to substrate.
Summary of the invention
The purpose of the present invention is to provide the electrodes that a kind of pair of fenifrothion has selective absorption, with selective absorption and
Detect fenifrothion.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of golden combination electrodes, enhanced sensitivity layer and oxidation included in the setting of gold electrode surfaces stacked above one another
Zirconium layer, the enhanced sensitivity layer include the compound and redox graphene of molybdenum disulfide and elemental gold.
Preferably, the mass ratio of the compound and redox graphene of molybdenum disulfide and elemental gold is in the enhanced sensitivity layer
(20~30): (40~60)；
Molybdenum disulfide and the mass ratio of elemental gold are (8~12) in the molybdenum disulfide and the compound of elemental gold: (10~
13)。
The present invention also provides a kind of preparation methods of gold combination electrode described in above-mentioned technical proposal, comprise the following steps:
(1) molybdenum disulfide water object, L-cysteine aqueous solution, aqueous solution of chloraurate and aqueous ascorbic acid is mixed to mix
It closes, carries out reduction reaction and obtain the compound of molybdenum disulfide and elemental gold；
(2) molybdenum disulfide and the compound of elemental gold, redox graphene and water are mixed, obtains mixed liquor；
(3) mixed liquor is coated on to the surface of gold electrode, obtains enhanced sensitivity layer in gold electrode surfaces after drying；
(4) gold electrode by the enhanced sensitivity layer modification that step (3) obtains is dipped in the mixed solution of basic zirconium chloride and potassium chloride,
Zirconium oxide layer is generated in its surface electro-deposition, obtains golden combination electrode.
Preferably, it is (0.5~1.5) mg that the molybdenum disulfide water, which mixes the quality of molybdenum disulfide and the volume ratio of water in object:
1mL；
The concentration of the L-cysteine aqueous solution is 3~7mmol/L；
The concentration of the aqueous solution of chloraurate is 10~15mmol/L；
The concentration of the aqueous ascorbic acid is 20~30mmol/L；
The molybdenum disulfide water mixes the body of object, L-cysteine aqueous solution, aqueous solution of chloraurate and aqueous ascorbic acid
Product is than being (8~12): (3~7): (3~7): (8~12).
Preferably, the time that the reduction reaction carries out is 1~5h.
Preferably, in the mixed liquor of the step (2), the concentration of the compound of molybdenum disulfide and elemental gold is 0.02~
0.05mg/mL, the concentration of redox graphene are 0.025~0.1mg/mL.
Preferably, in the mixed solution of the step (4), the concentration of basic zirconium chloride is 4~6mmol/L, potassium chloride it is dense
Degree is 0.05~0.15mmol/L.
Preferably, the electro-deposition is carried out using cyclic voltammetry, and the deposition voltage in the electrodeposition process is -1~
0.8V, sweep speed are 45~55mV/s, and deposition circle number is 5~20 circles.
The present invention also provides gold combination electrodes described in a kind of above-mentioned technical proposal in Electrochemical Detection fenifrothion
Using.
The present invention provides a kind of golden combination electrodes, enhanced sensitivity layer and oxidation included in the setting of gold electrode surfaces stacked above one another
Zirconium layer, the enhanced sensitivity layer include the compound and redox graphene of molybdenum disulfide and elemental gold；The oxygen reduction fossil
Black alkene is capable of increasing the specific surface area of electrode, promotes selective absorption of the zirconium oxide to fenifrothion, the sulphur on molybdenum disulfide surface
Can be with metallographic interaction, the common electric conductivity for improving electrode material.According to embodiment result it is found that the gold that the present invention obtains is answered
Composite electrode can successfully adsorb various concentration fenifrothion, and the setting of enhanced sensitivity layer can enhance the absorption to fenifrothion；Together
When, the fenifrothion of absorption can be removed by electrochemical method, realize the recycling of golden combination electrode；Furthermore
The gold combination electrode is higher than the compound of other similar structures to the selective absorption effect of fenifrothion from far away.
The present invention also provides the preparation methods of the golden combination electrode, and this method is easy to operate, easy to implement.
Detailed description of the invention
Fig. 1 is the cyclic voltammetry curve figure that titanium dioxide zirconium layer is deposited in 1 gold medal combination electrode of embodiment；
Fig. 2 is that 1 gold medal combination electrode of embodiment adsorbs the square wave volt-ampere curve after various concentration fenifrothion sample aqueous solution；
Fig. 3 modifies the cyclic voltammetry curve comparison diagram of the electrode of different enhanced sensitivity materials；
Fig. 4 is the square wave volt-ampere curve comparison diagram of 1 gold medal combination electrode of embodiment absorption front and back；
Fig. 5 is the regenerative process figure of 1 gold medal combination electrode of embodiment；
Fig. 6 is adsorption effect comparison chart of the electrode to variety classes substance for modifying different enhanced sensitivity materials；
Fig. 7 is that 2 gold medal combination electrode of embodiment adsorbs the square wave volt-ampere curve after various concentration fenifrothion sample aqueous solution；
Fig. 8 is that 3 gold medal combination electrode of embodiment adsorbs the square wave volt-ampere curve after various concentration fenifrothion sample aqueous solution.
Specific embodiment
The present invention provides a kind of golden combination electrodes, enhanced sensitivity layer and oxidation included in the setting of gold electrode surfaces stacked above one another
Zirconium layer, the enhanced sensitivity layer include the compound and redox graphene of molybdenum disulfide and elemental gold.
Gold electrode in gold combination electrode provided by the invention is the column gold electrode that diameter is 2mm.The present invention is to described
The source of gold electrode does not have any particular/special requirement, is using commercially available same specification gold electrode well-known to those skilled in the art
It can.
Gold combination electrode provided by the invention includes the enhanced sensitivity layer that gold electrode surfaces are arranged in, and the enhanced sensitivity layer includes two sulphur
Change molybdenum (MoS2) and elemental gold (Au) compound and redox graphene (rGO).In the present invention, in the enhanced sensitivity layer
The mass ratio of the compound and redox graphene of molybdenum disulfide and elemental gold is preferably (20~30): (40~60), more excellent
It is selected as 25:(45~55), most preferably 25:50；Molybdenum disulfide and elemental gold in the molybdenum disulfide and the compound of elemental gold
Mass ratio be preferably (8~12): (10~13), more preferably 10:11.82 pass through between the molybdenum disulfide and elemental gold
Au-S coordinate bond self assembly is combined.
Gold combination electrode provided by the invention includes the zirconium oxide layer that enhanced sensitivity layer surface is arranged in.
The present invention also provides a kind of preparation methods of gold combination electrode described in above-mentioned technical proposal, comprise the following steps:
(1) molybdenum disulfide water object, L-cysteine aqueous solution, aqueous solution of chloraurate and aqueous ascorbic acid is mixed to mix
It closes, carries out reduction reaction and obtain the compound of molybdenum disulfide and elemental gold；
(2) molybdenum disulfide and the compound of elemental gold, redox graphene and water are mixed, obtains mixed liquor；
(3) mixed liquor is coated on to the surface of gold electrode, obtains enhanced sensitivity layer in gold electrode surfaces after drying；
(4) gold electrode by the enhanced sensitivity layer modification that step (3) obtains is dipped in the mixed solution of basic zirconium chloride and potassium chloride,
Zirconium oxide layer is generated in its surface electro-deposition, obtains golden combination electrode.
The present invention need to pre-process gold electrode before carrying out electrode modification, then modify and increase in gold electrode surfaces again
Photosensitive layer.In the present invention, it sequentially includes pickling, polishing and washing that the pretreatment is preferred.In the specific embodiment of the invention,
The spent pickling acid washing lotion is the mixed liquor that 30wt% hydrogen peroxide and the 98wt% concentrated sulfuric acid are mixed to get with the volume ratio of 1:3；Institute
Stating pickling specifically is that gold electrode is submerged to 10~20min to carry out oxidation processes in pickling solution, to remove gold electrode surfaces
Oxidation film；The polishing is specially to be polished using 0.05 μm of alchlor；The washing is electric to gold using pure water
It is washed pole.After the washing, it is dry that the present invention preferably carries out nitrogen drying to the gold electrode.
Molybdenum disulfide water is mixed object, L-cysteine aqueous solution, aqueous solution of chloraurate and aqueous ascorbic acid by the present invention
Mixing carries out reduction reaction and obtains the compound of molybdenum disulfide and elemental gold.In the specific embodiment of the invention, the curing
It is the mixture for being dispersed in water molybdenum disulfide that molybdenum water, which mixes object, and the molybdenum disulfide is purchased from Nanjing Xian Feng nano material section
Skill Co., Ltd；The L-cysteine aqueous solution, aqueous solution of chloraurate and aqueous ascorbic acid are respectively will be corresponding molten
Matter is dissolved in the solution obtained after water.In the present invention, the molybdenum disulfide water mixes the quality of molybdenum disulfide and the volume of water in object
Than preferably (0.5~1.5) mg:1mL, more preferably 1mg:1mL；The concentration of the L-cysteine aqueous solution is preferably 3~
7mmol/L, more preferably 5mmol/L；The concentration of the aqueous solution of chloraurate is preferably 10~15mmol/L, more preferably 12~
13mmol/L；The concentration of the aqueous ascorbic acid is preferably 20~30mmol/L, more preferably 25mmol/L.In the present invention
In, the volume ratio that the molybdenum disulfide water mixes object, L-cysteine aqueous solution, aqueous solution of chloraurate and aqueous ascorbic acid is excellent
It is selected as (8~12): (3~7): (3~7): (8~12), more preferably 10:5:5:10.
Molybdenum disulfide water is first preferably mixed object by the present invention and L-cysteine aqueous solution mixes, and obtains primary mixes；Institute
It states mixing preferably to carry out under ultrasound condition, the frequency of the ultrasound is preferably 35~45KHz, more preferably 40KHz, described super
The time of sound is preferably 0.1~1h, more preferably 0.5h.
After obtaining the primary mixes, the present invention preferably mixes the primary mixes and aqueous solution of chloraurate, obtains
To two-stage mixture；The mixing preferably carries out under ultrasound condition, and the frequency of the ultrasound is preferably 35~45KHz, more excellent
It is selected as 40KHz, the time of the ultrasound is preferably 1~10min, more preferably 5min.
After obtaining the two-stage mixture, the aqueous ascorbic acid is preferably added dropwise in two-stage mixture by the present invention
Carry out reduction reaction.The present invention does not have any particular/special requirement to the rate of the dropwise addition, is preferably added dropwise in 1h all
Aqueous ascorbic acid.In the present invention, the time of the reduction reaction is from being added dropwise all Vitamin C sour waters
Start timing when solution, the time that the reduction reaction carries out is preferably 1~5h, more preferably 3~4h.In the present invention, institute
Stating reduction reaction is specially that gold chloride is restored by ascorbic acid, obtains gold nanoparticle, and the partial size of the gold nanoparticle is less than
100nm；The L-cysteine contains sulfydryl, can play a protective role to the gold nanoparticle of formation；Sulphur in molybdenum disulfide
With close Jin Nengli, it then follows hard and soft acid and base action principle obtains the compound of molybdenum disulfide and gold by self assembly coordinate bond.
The reduction reaction carries out at room temperature, without carrying out any additional heat treatment.The present invention uses should
Substep mixing mode gold chloride can be made evenly dispersed after, then with ascorbic acid carry out reduction reaction so that obtained Jenner
The granularity of rice corpuscles and distribution are more uniform.
After the reduction reaction, the present invention is preferably separated by solid-liquid separation the product system that reduction reaction obtains.The present invention
There is no any particular/special requirement to the embodiment of the separation of solid and liquid, can be realized and be separated by solid-liquid separation purpose.The present invention is excellent
The solid after the separation of solid and liquid is washed in choosing, and the number of the washing is preferably 3 times.The present invention preferably to washing after
Solid is dried, to obtain the compound (MoS of pure, dry molybdenum disulfide and elemental gold2-Au)；The drying
The temperature of processing is preferably 55~65 DEG C, and more preferably 60 DEG C；The time of the drying process is preferably 3~6h, more preferably
5h。
After obtaining molybdenum disulfide and the compound of elemental gold, the present invention by the molybdenum disulfide and the compound of elemental gold,
Redox graphene and water mixing, obtain mixed liquor.In the present invention, in the mixed liquor of the step (2), molybdenum disulfide and
The concentration of the compound of elemental gold is preferably 0.02~0.05mg/mL, more preferably 0.025mg/mL；Redox graphene
Concentration is preferably 0.025~0.1mg/mL, more preferably 0.05mg/mL.
After obtaining mixed liquor, the mixed liquor is coated on the surface of gold electrode by the present invention, in gold electrode surfaces after drying
Obtain enhanced sensitivity layer (MoS2-Au/rGO//Au).In the present invention, the coating is specially drop coating；The drying is specifically room
Temperature is dried.
After obtaining the gold electrode of enhanced sensitivity layer modification, the gold electrode that the enhanced sensitivity layer that step (3) obtains is modified is dipped in by the present invention
In the mixed solution of basic zirconium chloride and potassium chloride, zirconium oxide layer is generated in its surface electro-deposition, obtains golden combination electrode (ZrO2//
MoS2-Au/rGO//Au).In the present invention, the mixed solution of the basic zirconium chloride and potassium chloride is by basic zirconium chloride and chlorination
Potassium is dissolved in the mixed solution obtained after water；Concentration of the basic zirconium chloride in mixed solution is preferably 4~6mmol/L, more excellent
It is selected as 5mmol/L；Concentration of the potassium chloride in mixed solution is preferably 0.05~0.15mmol/L, more preferably
0.10mmol/L。
In the present invention, the electro-deposition specifically uses cyclic voltammetry to carry out, the deposition in the electrodeposition process
Voltage is preferably -1~0.8V, more preferably -0.5~0.5V；Sweep speed is preferably 45~55mV/s, more preferably 50mV/
s；Deposition circle number is preferably 5~20 circles, more preferably 10 circles.
After the electro-deposition, the present invention takes out golden combination electrode from mixed solution, obtains after washing clean
Golden combination electrode.
The present invention also provides a kind of application of the gold combination electrode described in above-mentioned technical proposal in detection fenifrothion.Make
For a preferred embodiment of the present invention, for the present invention using golden combination electrode as working electrode, platinum electrode is to electrode, calomel electrode
For reference electrode, 0.05~0.2M acetic acid: sodium-acetate buffer (pH=5.0~6.0) is three electrode bodies of electrolytic solution composition
System detects fenifrothion using square wave voltammetry, specific detection parameters setting are as follows: voltage: -0.15~0.2V sweeps speed:
62.5mV/s, time interval: 0.04s, jump rank current potential: 2.5mV, modulated amplitude: 20mV.The detection time of this method is about 15s
Left and right, greatly reduces detection time.
Golden combination electrode provided by the invention and its preparation method and application is carried out specifically below with reference to embodiment
It is bright, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Gold electrode is handled using the mixed liquor (1:3, v/v) of the hydrogen peroxide of 30wt% and the concentrated sulfuric acid composition of 98wt%
After 10min, with 0.05 μm of Al2O3Sanding and polishing, with water by electrode washing it is clean after, in aqueous solution with the frequency ultrasound of 40KHz
10min is dried with nitrogen spare；
By molybdenum disulfide powder MoS2The water for being configured to 1mg/mL concentration mixes object, and 10mL L-cysteine (5mmol/ is added
L 5mL gold chloride (HAuCl is added after the frequency ultrasound 0.5h of 40KHz in) aqueous solution4, 12mmol/L) and aqueous solution, with 40KHz
Frequency ultrasound 5min mix, it is water-soluble in 0.5h the ascorbic acid (25mmol/L) that 10mL now matches to be added dropwise under stirring condition
Liquid.Stirring 3h is continued thereafter with, reduction reaction product is centrifugated, washing separation three times, dry in 60 DEG C of baking ovens by obtained solid
4h obtains the compound (MoS of molybdenum disulfide and elemental gold2-Au)。
By rGO and MoS2- Au is configured to mixed aqueous solution (rGO:MoS2- Au=0.05mg/mL:0.025mg/mL), with
After the frequency ultrasound 10min of 40KHz, in 3 microlitres of drop coating to the gold electrode handled well, room temperature obtains being coated with enhanced sensitivity layer after drying
Electrode；
It is coated with the electrode washing of enhanced sensitivity layer, immerses and contains 5mmol/L basic zirconium chloride (ZrOCl2) and 0.1mol/L chlorine
Change in potassium (KCl) mixed aqueous solution, using cyclic voltammetry, sweeps fast 50mV/s, deposit 10 in -1.0~0.8V voltage range
Circle washes electrode then to get to golden combination electrode, is labeled as ZrO2//MoS2- Au/rGO//Au is dried with nitrogen.
The present invention has carried out performance characterization to the golden combination electrode that the present embodiment obtains, specific as described below:
(1) to deposition ZrO2The process of layer is detected, and cyclic voltammetry curve figure is as shown in Figure 1, a indicates electricity in Fig. 1
Deposition liquid is 0.1mol/LKCl solution, and b indicates that electrodeposit liquid is 5mmol/LZrOCl2With 0.1mol/LKCl mixed liquor.By Fig. 1
It is found that in 5mmol/L ZrOCl2In 0.1mol/LKCl deposition liquid, there is ZrOCl in -0.5~-1.0V range2Reduction
Peak, and do not occur in 0.1mol/LKCl solution, show the successful deposition of zirconium dioxide.
The formation mechenism of the reduction peak are as follows:
ZrOCl2+e-→ZrOCl+Cl-；
2ZrOCl+2H2O→2ZrO2+2HCl+H2。
(2) by the golden combination electrode be suspended in fenifrothion sample aqueous solution (sample concentration be respectively 0ng/mL,
20ng/mL, 50ng/mL, 100ng/mL, 200ng/mL, 400ng/mL, 600ng/mL) in adsorb 10min, taking-up is rinsed with water
After carry out electro-chemical test；
Electro-chemical test: using square wave voltammetry (voltage: -0.15~0.2V sweeps speed: 62.5mV/s, time interval:
0.04s, jump rank current potential: 2.5mV, modulated amplitude: 20mV), it is measured in three-electrode system, using golden combination electrode as work electricity
Pole, platinum electrode are to electrode, and calomel electrode is that reference electrode forms three-electrode system, and electrolytic solution is 0.2mol/L acetic acid: vinegar
Sour sodium buffer (pH=5.0) records square wave voltammetric scan curve and peak response current value, as a result as shown in Fig. 2, Fig. 2 is
1 gold medal combination electrode of embodiment adsorbs the square wave volt-ampere curve after various concentration fenifrothion sample aqueous solution, in Fig. 2 from bottom to up
It is followed successively by 0ng/mL, 20ng/mL, 50ng/mL, 100ng/mL, 200ng/mL, 400ng/mL, 600ng/mL, linear equation difference
Are as follows: I=0.01C+0.200, detection are limited to 8.6ng/mL.By Fig. 2 result it is found that gold combination electrode provided by the invention being capable of spirit
The quick fenifrothion for detecting various concentration.
(3) to golden combination electrode, and the gold of adsorption treatment has been carried out in 600ng/mL fenifrothion sample aqueous solution
Combination electrode and ZrO2/ Au electrode detection, cyclic voltammetry curve figure is as shown in figure 3, a is unadsorbed fenifrothion in Fig. 3
Golden combination electrode, b and c are respectively the ZrO for having adsorbed fenifrothion2/ Au electrode and golden combination electrode.From the figure 3, it may be seen that gold is compound
There is its redox peaks after having adsorbed fenifrothion at 0.07V and 0.04V in electrode, it was demonstrated that this golden combination electrode can
Absorption fenifrothion detects it；Au electrode is in modification rGO/MoS2Absorption after-Au composite material, to fenifrothion
Effect enhancing, it was demonstrated that the effect of enhanced sensitivity of golden combination electrode.Redox peaks at 0.07V and 0.04V are the benzene of fenifrothion
The redox peaks of nitro, mechanism are as follows:
(4) to golden combination electrode, and the gold of adsorption treatment has been carried out in 600ng/mL fenifrothion sample aqueous solution
Combination electrode is detected, and dissolution square wave volt-ampere curve is as shown in figure 4, a is the golden compound electric of unadsorbed fenifrothion in Fig. 4
Pole, b are the golden combination electrode for having adsorbed fenifrothion.As shown in Figure 4, the golden combination electrode of preparation has absorption to fenifrothion
Effect, can be used square wave voltammetry and is detected.
(5) the golden combination electrode dissolves out electrode after having adsorbed 600ng/mL fenifrothion sample, different molten
Square wave volt-ampere curve when outdegree is as shown in Figure 5.As shown in Figure 5, as scanning times increase, peak current signal gradually disappears
It loses, shows fenifrothion-ZrO2Compound keys dissociate the reuse, it can be achieved that electrode.
(6) by the golden combination electrode, ZrO2/ Au electrode and ZrO2/MoS2- Au/Au electrode adsorb respectively fenifrothion with
And parathion-methyl, parathion, omethoate, thimet, Azodrin and the nitrobenzene similar with its structure, selective evaluation knot
Fruit is as shown in Figure 6.It will be appreciated from fig. 6 that the gold combination electrode is significantly larger than other electrodes to the responsiveness of fenifrothion, and right
The responsiveness of fenifrothion is significantly larger than the similar drug of other structures, shows the identification fenifrothion for the property of can choose, thus
Realize qualitative test.
(7) the present embodiment detects fenifrothion in tap water using standard addition absorption method, result such as 1 institute of table
Show.
The determination of recovery rates result of fenifrothion in 1 tap water of table
As seen from the results in Table 1, use the rate of recovery of fenifrothion in tap water obtained by standard addition method for 91.0~
100%.
Embodiment 2
Gold electrode is handled using the mixed liquor (1:3, v/v) of the hydrogen peroxide of 30wt% and the concentrated sulfuric acid composition of 98wt%
After 15min, with 0.05 μm of Al2O3Sanding and polishing, with water by electrode washing it is clean after, in aqueous solution with the frequency ultrasound of 40KHz
10min is dried with nitrogen spare；
By molybdenum disulfide powder MoS2The water for being configured to 1mg/mL concentration mixes object, and 5mL L-cysteine (5mmol/ is added
L 5mL gold chloride (HAuCl is added after the frequency ultrasound 0.5h of 40KHz in) aqueous solution4, 12mmol/L) and aqueous solution, with 40KHz
Frequency ultrasound 5min mix, it is water-soluble in 0.5h the ascorbic acid (25mmol/L) that 10mL now matches to be added dropwise under stirring condition
Liquid.Stirring 3h is continued thereafter with, reduction reaction product is centrifugated, washing separation three times, dry in 60 DEG C of baking ovens by obtained solid
4h obtains the compound (MoS of molybdenum disulfide and elemental gold2-Au)。
By rGO and MoS2- Au is configured to mixed aqueous solution (rGO:MoS2- Au=0.025mg/mL:0.025mg/mL), with
After the frequency ultrasound 10min of 40KHz, in 4 microlitres of drop coating to the gold electrode handled well, room temperature obtains being coated with enhanced sensitivity layer after drying
Electrode；
It is coated with the electrode washing of enhanced sensitivity layer, immerses and contains 5mmol/L basic zirconium chloride (ZrOCl2) and 0.1mol/L chlorine
Change in potassium (KCl) mixed aqueous solution, using cyclic voltammetry, sweeps fast 50mV/s, deposit 5 in -1.0~0.8V voltage range
Circle, subsequent electrode washing are labeled as ZrO to get to golden combination electrode2//MoS2- Au/rGO//Au is dried with nitrogen.
The present invention has carried out performance detection to the golden combination electrode that the present embodiment obtains, specific as described below:
The golden combination electrode is suspended in fenifrothion sample aqueous solution, and (sample concentration is respectively 0ng/mL, 20ng/
ML, 50ng/mL, 100ng/mL, 200ng/mL, 400ng/mL, 600ng/mL) in adsorb 5min, taking-up be rinsed with water after carry out
Electro-chemical test；
Electro-chemical test: using square wave voltammetry (voltage: -0.15~0.2V sweeps speed: 62.5mV/s, time interval:
0.04s, jump rank current potential: 2.5mV, modulated amplitude: 20mV), it is measured in three-electrode system, using golden combination electrode as work electricity
Pole, platinum electrode are to electrode, and calomel electrode is that reference electrode forms three-electrode system, and electrolytic solution is 0.05mol/L acetic acid: vinegar
Sour sodium buffer (pH=6.0) records square wave voltammetric scan curve and peak response current value, as a result as shown in fig. 7, Fig. 7 is
2 gold medal combination electrode of embodiment adsorbs the square wave volt-ampere curve after various concentration fenifrothion sample aqueous solution, in Fig. 7 from bottom to up
It is followed successively by 0ng/mL, 20ng/mL, 50ng/mL, 100ng/mL, 200ng/mL, 400ng/mL, 600ng/mL, linear equation difference
Are as follows: I=0.008C+0.115, detection are limited to 10.6ng/mL.By Fig. 7 result it is found that gold combination electrode provided by the invention can
Sensitively detect the fenifrothion of various concentration.
Embodiment 3
Gold electrode is handled using the mixed liquor (1:3, v/v) of the hydrogen peroxide of 30wt% and the concentrated sulfuric acid composition of 98wt%
After 20min, with 0.05 μm of Al2O3Sanding and polishing, with water by electrode washing it is clean after, in aqueous solution with the frequency ultrasound of 40KHz
10min is dried with nitrogen spare；
By molybdenum disulfide powder MoS2The water for being configured to 1mg/mL concentration mixes object, and 5mL L-cysteine (5mmol/ is added
L 5mL gold chloride (HAuCl is added after the frequency ultrasound 0.5h of 40KHz in) aqueous solution4, 12mmol/L) and aqueous solution, with 40KHz
Frequency ultrasound 5min mix, it is water-soluble in 0.5h the ascorbic acid (25mmol/L) that 10mL now matches to be added dropwise under stirring condition
Liquid.Stirring 3h is continued thereafter with, reduction reaction product is centrifugated, washing separation three times, dry in 60 DEG C of baking ovens by obtained solid
4h obtains the compound (MoS of molybdenum disulfide and elemental gold2-Au)。
By rGO and MoS2- Au is configured to mixed aqueous solution (rGO:MoS2- Au=0.05mg/mL:0.05mg/mL), with
After the frequency ultrasound 10min of 40KHz, in 4 microlitres of drop coating to the gold electrode handled well, room temperature obtains being coated with enhanced sensitivity layer after drying
Electrode；
It is coated with the electrode washing of enhanced sensitivity layer, immerses and contains 5mmol/L basic zirconium chloride (ZrOCl2) and 0.1mol/L chlorine
Change in potassium (KCl) mixed aqueous solution, using cyclic voltammetry, sweeps fast 50mV/s, deposit 20 in -1.0~0.8V voltage range
Circle, subsequent electrode washing are labeled as ZrO to get to golden combination electrode2//MoS2- Au/rGO//Au is dried with nitrogen.
The present invention has carried out performance detection to the golden combination electrode that the present embodiment obtains, specific as described below:
The golden combination electrode is suspended in fenifrothion sample aqueous solution, and (sample concentration is respectively 0ng/mL, 20ng/
ML, 50ng/mL, 100ng/mL, 200ng/mL, 400ng/mL, 600ng/mL) in adsorb 12min, taking-up be rinsed with water after carry out
Electro-chemical test；
Electro-chemical test: using square wave voltammetry (voltage: -0.15~0.2V sweeps speed: 62.5mV/s, time interval:
0.04s, jump rank current potential: 2.5mV, modulated amplitude: 20mV), it is measured in three-electrode system, using golden combination electrode as work electricity
Pole, platinum electrode are to electrode, and calomel electrode is that reference electrode forms three-electrode system, and electrolytic solution is 0.05mol/L acetic acid: vinegar
Sour sodium buffer (pH=6.0) records square wave voltammetric scan curve and peak response current value, as a result as shown in figure 8, Fig. 8 is
3 gold medal combination electrode of embodiment adsorbs the square wave volt-ampere curve after various concentration fenifrothion sample aqueous solution, in Fig. 8 from bottom to up
It is followed successively by 0ng/mL, 20ng/mL, 50ng/mL, 100ng/mL, 200ng/mL, 400ng/mL, 600ng/mL, linear equation difference
Are as follows: I=0.005C+0.001, detection are limited to 12.5ng/mL.By Fig. 8 result it is found that gold combination electrode provided by the invention can
Sensitively detect the fenifrothion of various concentration.
As seen from the above embodiment, the present invention provides a kind of golden combination electrode, the enhanced sensitivity layer comprising stacked above one another setting
And zirconium oxide layer, the enhanced sensitivity layer include the compound and redox graphene of molybdenum disulfide and elemental gold；The reduction
Graphene oxide is capable of increasing the specific surface area of electrode, promotes selective absorption of the zirconium oxide to fenifrothion, molybdenum disulfide table
The sulphur in face can be with metallographic interaction, the common electric conductivity for improving electrode material.According to embodiment result it is found that the present invention obtains
Golden combination electrode can successfully adsorb various concentration fenifrothion, and the setting of enhanced sensitivity layer can enhance the suction to fenifrothion
It is attached；Meanwhile, it is capable to the fenifrothion of absorption be removed by electrochemical method, realize the recycling of golden combination electrode；
Furthermore the gold combination electrode is higher than other similar structure electrodes, the electricity to the selective absorption effect of fenifrothion from far away
Other compounds are also extremely much higher than to the response sensitivity of fenifrothion, so there is significant selectivity to fenifrothion, are
Its accurate qualitative, quantitative measurement provides basis.
The present invention also provides the preparation methods of the golden combination electrode, and this method is easy to operate, easy to implement.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of gold combination electrode, included in the enhanced sensitivity layer and zirconium oxide layer of the setting of gold electrode surfaces stacked above one another, the enhanced sensitivity
Layer includes the compound and redox graphene of molybdenum disulfide and elemental gold；
The preparation method of the gold combination electrode, comprises the following steps:
(1) molybdenum disulfide water object, L-cysteine aqueous solution, aqueous solution of chloraurate and aqueous ascorbic acid is mixed to mix, into
Row reduction reaction obtains the compound of molybdenum disulfide and elemental gold；
(2) molybdenum disulfide and the compound of elemental gold, redox graphene and water are mixed, obtains mixed liquor；
(3) mixed liquor is coated on to the surface of gold electrode, obtains enhanced sensitivity layer in gold electrode surfaces after drying；
(4) gold electrode by the enhanced sensitivity layer modification that step (3) obtains is dipped in the mixed solution of basic zirconium chloride and potassium chloride, at it
Surface electro-deposition generates zirconium oxide layer, obtains golden combination electrode.
2. gold combination electrode according to claim 1, which is characterized in that molybdenum disulfide and elemental gold in the enhanced sensitivity layer
The mass ratio of compound and redox graphene is (20~30): (40~60)；
Molybdenum disulfide and the mass ratio of elemental gold are (8~12): (10~13) in the molybdenum disulfide and the compound of elemental gold.
3. the preparation method of gold combination electrode described in claim 1~2 any one, comprises the following steps:
(1) molybdenum disulfide water object, L-cysteine aqueous solution, aqueous solution of chloraurate and aqueous ascorbic acid is mixed to mix, into
Row reduction reaction obtains the compound of molybdenum disulfide and elemental gold；
(2) molybdenum disulfide and the compound of elemental gold, redox graphene and water are mixed, obtains mixed liquor；
(3) mixed liquor is coated on to the surface of gold electrode, obtains enhanced sensitivity layer in gold electrode surfaces after drying；
(4) gold electrode by the enhanced sensitivity layer modification that step (3) obtains is dipped in the mixed solution of basic zirconium chloride and potassium chloride, at it
Surface electro-deposition generates zirconium oxide layer, obtains golden combination electrode.
4. preparation method according to claim 3, which is characterized in that the molybdenum disulfide water mixes the matter of molybdenum disulfide in object
Amount and the volume ratio of water are (0.5~1.5) mg:1mL；
The concentration of the L-cysteine aqueous solution is 3~7mmol/L；
The concentration of the aqueous solution of chloraurate is 10~15mmol/L；
The concentration of the aqueous ascorbic acid is 20~30mmol/L；
The molybdenum disulfide water mixes the volume ratio of object, L-cysteine aqueous solution, aqueous solution of chloraurate and aqueous ascorbic acid
For (8~12): (3~7): (3~7): (8~12).
5. preparation method according to claim 3 or 4, which is characterized in that the time that the reduction reaction carries out is 1~
5h。
6. preparation method according to claim 3, which is characterized in that in the mixed liquor of the step (2), molybdenum disulfide and
The concentration of the compound of elemental gold is 0.02~0.05mg/mL, and the concentration of redox graphene is 0.025~0.1mg/mL.
7. preparation method according to claim 3, which is characterized in that in the mixed solution of the step (4), basic zirconium chloride
Concentration be 4~6mmol/L, the concentration of potassium chloride is 0.05~0.15mmol/L.
8. preparation method according to claim 3 or 7, which is characterized in that the electro-deposition is carried out using cyclic voltammetry,
Deposition voltage in the electrodeposition process is -1~0.8V, and sweep speed is 45~55mV/s, and deposition circle number is 5~20 circles.
9. application of the gold combination electrode in Electrochemical Detection fenifrothion described in claim 1~2 any one.
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| CN103743804A (en) * | 2014-01-15 | 2014-04-23 | 湖南省茶叶研究所 | Organic phosphorus electrochemical biosensor based on adsorption of nano particles |
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| CN103743804A (en) * | 2014-01-15 | 2014-04-23 | 湖南省茶叶研究所 | Organic phosphorus electrochemical biosensor based on adsorption of nano particles |
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