CN102706936A - Preparation method of copper-copper oxide composite electrode - Google Patents
Preparation method of copper-copper oxide composite electrode Download PDFInfo
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Abstract
The invention discloses a preparation method of a copper-copper oxide composite electrode, which comprises the following steps: a. cleaning of a copper rod; b. preparation of a cupric hydroxide suspension; and c. preparation of the composite electrode: adding a prepared alkali (b) solution in a reaction kettle, immersing the copper rod in the alkali (b) solution, closing the reaction kettle, reacting at 60-80 DEG C for 2-6 hours, cooling to room temperature, cleaning the electrode, and drying at room temperature, thereby obtaining the composite electrode. The mass/area ratio of the copper oxide-copper electrode is 0.0063-0.0134g/cm<2>. Compared with the prior art, the invention has the advantages of high reproducibility, low energy consumption, low minimum limit of detected ions (0.4 mu M), high response stability during ion monitoring and low synthesis cost, is simple to operate, and is suitable for industrial large-scale preparation; and the prepared copper oxide nano belt is uniformly coated on the copper electrode surface, and the electrode with high specific area can be used as a sensor material to sufficiently contact the measured object, so that the electrocatalytic reaction is sufficient and efficient.
Description
Technical field
The invention belongs to the preparation method of electrode, belong to the preparation method of combination electrode especially.
Background technology
Along with the development of advancing by leaps and bounds of making rapid progress of science and technology, can not be satisfied with practical demand gradually as the traditional electrode of sensor.Traditional sensor electrode has glass carbon electricity, gold electrode etc., and in use there is number of drawbacks in they.For example this type of electrode all need pass through treatment steps such as polishing, modification, drying before use, and these treatment steps directly influence electrochemical response.Therefore also just cause when modifying same material, electrode of the same race is carried out twice same steps as handle, and the result can be different.Moreover as noble metal electrode, its price is also relatively more expensive.
Nano-sensor (Nano Senser) is a kind of sensor technology of emerging forward position, and it is in space flight, machinery; Instrument and meter, automobile making, oily vapour exploration; Electronic engineering and medical device industry all have extensive use, are chosen as one of following six big frontier science and technology of influence by European Union.
With body material and nano material produced with combination sensor electrode, more and more become the focus of sensor field in recent years.And copper becomes field preferred material for this reason as a kind of cheapness, material that electric conductivity is high.Copper is commonly used to the substrate as compound substance, grows inhomogeneous nano material in the above, thereby produces dissimilar materials.
So far, though the process for making of many copper electrodes is arranged, generally all comparatively numerous and diverse.Chinese patent 200910146910.X provides the manufacturing approach of copper electrode structure; Chinese patent CN200710029108.3, a kind of copper electrode paste and manufacturing approach thereof are disclosed; Chinese patent CN01216465.8 provides a kind of new copper/copper sulfate eletrode synthetic method; Chinese patent 200910050292.9 provides a kind of method that forms white assembling corrosion inhibition film on the copper electrode surface or the like; All relevant copper electrode preparations only are to the processing above the body material; All do not relate to field of nanometer technology; Detect usefulness and far can not be satisfied with practical demand, and its preparation process is comparatively complicated.
Summary of the invention
In view of above defective, the present invention provides a kind of copper base composite electric utmost point, and this electrode is made simple, directly makes cupric oxide nano structure length on copper rod with hydro-thermal method, and the copper that obtains-cupric oxide combination electrode can be used as sensor and directly is used for the material detection.For the attainment of one's purpose, the preparation method of a kind of copper provided by the invention-cupric oxide combination electrode may further comprise the steps:
The clean operation of a, copper rod:
Under ultrasonic cleaning, clean copper rod with acetone, ethanol, watery hydrochloric acid, distilled water successively;
The preparation section of b, the muddy liquid of Kocide SD:
1) under room temperature, stirring condition, (a) is dissolved in the distilled water kind with a certain amount of alkali, and stirring is fully dissolved it and got final product;
2) under room temperature, stirring condition, a certain amount of cupric salt is dissolved in the distilled water, stirring is fully dissolved it and is got final product;
3) above-mentioned two kinds of solution are mixed, and put into cleaned copper rod, ultrasonic a period of time, the mol ratio of copper ion and hydroxide ion is 1: 5-8;
The preparation section of c, combination electrode:
In agitated reactor, add alkali (b) the property solution for preparing, the more above-mentioned copper rod of handling well is immersed, agitated reactor is airtight, under 60-80 ℃ situation, reacted 2-6 hour, be cooled to room temperature, cleaning electrode, drying at room temperature gets final product.
Said alkali (a) and (b) solution is sodium hydroxide solution.
Described cupric salt is Cu (NO
3)
23H
2O.
The concentration of described sodium hydroxide solution is 0.05M.
Described mantoquita copper ion concentration is 0.01M.
In turbid solution, copper rod being carried out ultrasonic time is 10-20 minute.
Hydro-thermal method of the present invention is a kind of wet chemical method of in closed container, accomplishing.Be particularly in airtight high-temperature high-pressure reaction kettle, adopt water to do reaction dissolvent,, produce a hyperbaric environment and a kind of effective ways of carrying out material preparation through the reacting by heating system.The characteristics that hydro-thermal method is produced are product purity height, good dispersion, good crystalline and may command, and production cost is low, and reappearance is very good, can reach more than 95%.
The copper rod of using among the present invention, because its good electrical conductivity, cheap price, and can be widely used in copper the preparation of heterojunction structure electrode of the various different nano materials that are substrate.
The present invention selects copper rod as the substrate grown cupric oxide, is based on copper rod under alkaline environment, and the high pressure heating can generate one deck cupric oxide nano structure on the surface.Electrode to the present invention's preparation carries out the detection of electrochemical sensing character, in the sodium hydroxide solution of pH=13, detects hydrazine, and its result shows that this electrode pair hydrazine has good electrochemical catalysis effect really, and the lowest detection limit is 0.0004mM, and passes through formula
The surface coverage concentration of having calculated the combination electrode of embodiment 1 preparation is 9 * 10
-8Mol cm
-2, meet data in literature, thereby can be used as sensor.
The present invention compared with prior art has the reappearance height, and material high detection performance is easy and simple to handle, and it is low to consume energy, and synthetic cost is low, is suitable for industry and goes up mass preparation; The prepared cupric oxide nano band that goes out has bigger specific surface area, can fully contact with determinand as sensor material, makes electrocatalytic reaction fully efficient.
Description of drawings
Fig. 1 is the copper of embodiment 1 preparation--powder x-ray diffraction (XRD) figure of cupric oxide composite electrode.
Fig. 2 is copper--the electron scanning micrograph (SEM) of the low enlargement ratio of cupric oxide composite electrode of embodiment 1 preparation.
Fig. 3 is copper--the electron scanning micrograph (SEM) of the high enlargement ratio of cupric oxide composite electrode of embodiment 1 preparation.
Fig. 4 for embodiment 1 preparation copper--the cupric oxide composite electrode carries out the cyclic voltammogram (CV) of Electrochemical Detection to hydrazine.
Curve 3 for embodiment 1 preparation copper--the cupric oxide combination electrode does not add the cyclic voltammetry curve of hydrazine in the sodium hydroxide solution of pH=13.
Curve 4 for embodiment 1 preparation copper--the cupric oxide combination electrode has added the cyclic voltammetry curve of 0.0667mM hydrazine in the sodium hydroxide solution of pH=13.
Curve 5 for embodiment 1 preparation copper--the cupric oxide combination electrode has added the cyclic voltammetry curve of 0.5336mM hydrazine in the sodium hydroxide solution of pH=13.
Fig. 5 is the copper of embodiment 1 preparation--the cupric oxide composite electrode detects the time current curve (i-t) of hydrazine.Detection is limited to 0.4 μ M, and the range of linearity is 1-1150mM.
The practical implementation method
Below in conjunction with accompanying drawing and practical implementation method, to preparation process of the present invention, method and electrochemical applications are done further explanation:
Under room temperature, magnetic agitation condition, with 0.0858g nitric hydrate copper dissolution (two parts) in 20ml distilled water, the 0.04g dissolution of sodium hydroxide in 20ml distilled water, under the magnetic agitation is mixed two solution, process the muddy liquid of Kocide SD.Be 2.5mm with cross-sectional area then
2, length is that 4cm copper rod clean is good, and is immersed in the above-mentioned muddy liquid ultrasonic 10 minutes.
The a sodium hydroxide solution for preparing is transferred in the 60mL agitated reactor, then, will in muddy liquid, be transferred to agitated reactor in the solution by the copper rod of ultrasonic mistake.Tighten kettle cover, reaction is 4 hours in 80 ℃ baking oven.After reaction finishes, take out still and naturally cool to room temperature, on copper rod, be coated with one deck cupric oxide; Use distilled water flushing; Having the copper rod of cupric oxide to dry naturally growth, promptly make copper--the cupric oxide combination electrode, cupric oxide is 0.0132g/cm with the mass/area ratio of copper electrode
2
Ultrasonic time will be controlled at about 10-20 minute, purpose 1) activation copper rod surface; 2) generate the copper oxide nano particle seed on the copper rod surface.
The pattern of made electrode is as shown in Figure 2, cupric oxide is band shape and is arranged on the copper rod.
Under room temperature, magnetic agitation condition, in 20ml distilled water, be 2.5mm with cross-sectional area then with the 0.04g dissolution of sodium hydroxide
2, length is that 4cm copper rod clean is good, directly copper rod is put into sodium hydroxide solution, and changes in the agitated reactor together.Tighten kettle cover, reaction is 4 hours in 80 ℃ baking oven.After reaction finishes, take out still and naturally cool to room temperature, on copper rod, be coated with one deck cupric oxide; Use distilled water flushing; Have the copper rod of cupric oxide to dry naturally growth, promptly make copper--the cupric oxide combination electrode, but gained meet electrode surface only seldom covering one deck cupric oxide nano band.
Embodiment 3
Under room temperature, magnetic agitation condition, 0.0858g nitric hydrate copper dissolution in 20ml distilled water, in 20ml distilled water, under the magnetic agitation is mixed the 0.08g dissolution of sodium hydroxide with two solution, process the muddy liquid of Kocide SD.Be 2.5mm with cross-sectional area then
2, length is that 4cm copper rod clean is good, and is immersed in the above-mentioned muddy liquid ultrasonic 10 minutes.
The a sodium hydroxide solution for preparing is transferred in the 60mL agitated reactor, then, will in muddy liquid, be transferred to agitated reactor in the solution by the copper rod of ultrasonic mistake.Tighten kettle cover, reaction is 4 hours in 80 ℃ baking oven.After reaction finishes, take out still and naturally cool to room temperature, on copper rod, be coated with one deck cupric oxide; Use distilled water flushing; Having the copper rod of cupric oxide to dry naturally growth, promptly make copper--the cupric oxide combination electrode, cupric oxide is 0.0134g/cm with the mass/area ratio of copper electrode
2
The pattern of made electrode is banded, and is almost equal to the response and the embodiment 1 made electrode of hydrazine solution.
Embodiment 4
Under room temperature, magnetic agitation condition, 0.0858g nitric hydrate copper dissolution in 20ml distilled water, in 20ml distilled water, under the magnetic agitation is mixed the 0.04g dissolution of sodium hydroxide with two solution, process the muddy liquid of Kocide SD.Be 2.5mm with cross-sectional area then
2, length is that 4cm copper rod clean is good, and is immersed in the above-mentioned muddy liquid ultrasonic 10 minutes.
The a sodium hydroxide solution for preparing is transferred in the 60mL agitated reactor, then, will in muddy liquid, be transferred to agitated reactor in the solution by the copper rod of ultrasonic mistake.Tighten kettle cover, reaction is 4 hours in 60 ℃ baking oven.After reaction finishes, take out still and naturally cool to room temperature, on copper rod, be coated with one deck cupric oxide; Use distilled water flushing; Having the copper rod of cupric oxide to dry naturally growth, promptly make copper--the cupric oxide combination electrode, cupric oxide is 0.0063g/cm with the mass/area ratio of copper electrode
2
Embodiment 5
Under room temperature, magnetic agitation condition, 0.0858g nitric hydrate copper dissolution in 20ml distilled water, in 20ml distilled water, under the magnetic agitation is mixed the 0.04g dissolution of sodium hydroxide with two solution, process the muddy liquid of Kocide SD.Be 2.5mm with cross-sectional area then
2, length is that 4cm copper rod clean is good, and is immersed in the above-mentioned muddy liquid ultrasonic 10 minutes.
The a sodium hydroxide solution for preparing is transferred in the 60mL agitated reactor, then, will in muddy liquid, be transferred to agitated reactor in the solution by the copper rod of ultrasonic mistake.Tighten kettle cover, reaction is 4 hours in 100 ℃ baking oven.After reaction finishes, take out still and naturally cool to room temperature, on copper rod, be coated with one deck cupric oxide; Use distilled water flushing; Having the copper rod of cupric oxide to dry naturally growth, promptly make copper--the cupric oxide combination electrode, cupric oxide is 0.0134g/cm with the mass/area ratio of copper electrode
2
Embodiment 6
Under room temperature, magnetic agitation condition, 0.0858g nitric hydrate copper dissolution in 20ml distilled water, is dissolved in 0.1ml ammoniacal liquor (mass concentration is 25%) in the 20ml distilled water, under the magnetic agitation two solution are mixed, process bivalent cupric ion solution.Be 2.5mm with cross-sectional area then
2, length is that 4cm copper rod clean is good, and immerses above-mentioned solution, ultrasonic 10 minutes.
The a sodium hydroxide solution for preparing is transferred in the 60mL agitated reactor, then, will in bivalent cupric ion solution, be transferred to agitated reactor in the solution by the copper rod of ultrasonic mistake.Tighten kettle cover, reaction is 4 hours in 80 ℃ baking oven.After reaction finishes, take out still and naturally cool to room temperature, on copper rod, be coated with one deck cupric oxide, use distilled water flushing, have the copper rod of cupric oxide to dry naturally growth, promptly make copper--the cupric oxide combination electrode.Gained appearance is shaped as slab-like under ESEM, to the electrochemical response of hydrazine not as banded.
Embodiment 7 (electrochemical applications)
With the electrode that embodiment 1 prepares, directly be used for doing electrode, do the electrochemical properties test., as electrolyte hydrazine is detected with 0.1MNaOH solution.
Get 6ml 0.1M NaOH solution and put into electrolytic tank, the electrode for preparing among the embodiment 1 as working electrode, is connected three-electrode system, open electrochemical workstation as electrolyte solution.Configure correlation parameter, when not adding hydrazine, survey cyclic voltammetry curve (curve 3 among Fig. 4), the hydrazine of then getting 40 μ L0.01M with microliter syringe injects electrolytic tank, measure curve 4 among Fig. 4, the concentration of hydrazine is 0.0667mM in the electrolytic tank.Comparison curves 3 and 4 can find at electromotive force 0.4V, have corresponding big electric current to change; Explain that this electrode pair hydrazine has electrochemical response; Continue to add the hydrazine of 40 μ L 0.07M again, the cyclic voltammetry curve 5 that records has stronger current-responsive at electromotive force 0.4V, and this moment, current-responsive was about 8 times in the curve 4; And this moment, the concentration in the electrolytic tank was 0.5336mM, explained that response current and hydrazine concentration are linear.
For verificating current response is to be caused but not the direct effect of copper rod the invention provides the contrast experiment by the cupric oxide nano band.The copper rod that is about to clean do not grow cupric oxide nano belt and same size detects hydrazine as working electrode; The result finds after having added 40 μ L concentration to be the 0.01mM hydrazine (curve 2 among Fig. 4); Almost do not have current-responsive at electromotive force 0.4V place, go curve almost to overlap with the cyclic voltammetric that does not add hydrazine (curve 1 among Fig. 4).This proves that fully electrode pair hydrazine provided by the invention has electrochemical response.
For further studying electrochemical properties of the present invention, also be time current curve figure (Fig. 5).Promptly, add the hydrazine of identical or different concentration, whenever add a capital and produce a step, till no longer producing step whenever at a distance from 50 seconds.The electrode pair hydrazine response time that records the embodiment of the invention one preparation is detected and is limited to 0.4 μ M on average less than 4 seconds, and the range of linearity is 1-1150mM, shows that this electrode can be used as the electrochemical sensor of hydrazine.
Claims (5)
1. the preparation method of copper-cupric oxide combination electrode may further comprise the steps:
The preparation method of copper-cupric oxide combination electrode may further comprise the steps:
The clean operation of a, copper rod:
Under ultrasonic cleaning, clean copper rod with acetone, ethanol, watery hydrochloric acid, distilled water successively;
The preparation section of b, the muddy liquid of Kocide SD:
1) under room temperature, stirring condition, (a) is dissolved in the distilled water kind with a certain amount of alkali, and stirring is fully dissolved it and got final product;
2) under room temperature, stirring condition, a certain amount of cupric salt is dissolved in the distilled water, stirring is fully dissolved it and is got final product;
3) above-mentioned two kinds of solution are mixed, and put into cleaned copper rod, ultrasonic a period of time, the mol ratio of copper ion and hydroxide ion is 1: 5-8;
The preparation section of c, combination electrode:
In agitated reactor, add alkali (b) the property solution for preparing, the more above-mentioned copper rod of handling well is immersed, agitated reactor is airtight, under 60-80 ℃ situation, reacted 2-6 hour, be cooled to room temperature, cleaning electrode, drying at room temperature gets final product.
2. the preparation method of copper according to claim 1-cupric oxide combination electrode is characterized in that: said alkali (a) and (b) solution is sodium hydroxide solution.
3. the preparation method of copper according to claim 1-cupric oxide combination electrode is characterized in that: described cupric salt is Cu (NO
3)
23H
2O.
4. the preparation method of copper according to claim 1-cupric oxide combination electrode is characterized in that: the concentration of described sodium hydroxide solution is 0.05M.
5. the preparation method of copper according to claim 1-cupric oxide combination electrode is characterized in that: described mantoquita copper ion concentration is 0.01M.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058260A (en) * | 2012-12-29 | 2013-04-24 | 安徽师范大学 | Preparation method for belt-shaped silver oxide nano array |
| CN103578785A (en) * | 2013-10-16 | 2014-02-12 | 安徽师范大学 | Multi-hole nanometer copper oxide composite material, method for preparing same, supercapacitor electrodes and supercapacitor |
| CN103578784A (en) * | 2013-10-16 | 2014-02-12 | 安徽师范大学 | Nanometer copper oxide composite material and preparation method thereof and super-capacitor electrode and super-capacitor |
| CN107552069A (en) * | 2017-09-07 | 2018-01-09 | 张家港市汇鼎新材料科技有限公司 | A kind of preparation method of Research of Silver Copper Oxide Composite |
| CN112941556A (en) * | 2021-01-27 | 2021-06-11 | 国家纳米科学中心 | Copper-based solid material and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058260A (en) * | 2012-12-29 | 2013-04-24 | 安徽师范大学 | Preparation method for belt-shaped silver oxide nano array |
| CN103058260B (en) * | 2012-12-29 | 2014-10-15 | 安徽师范大学 | Preparation method for belt-shaped silver oxide nano array |
| CN103578785A (en) * | 2013-10-16 | 2014-02-12 | 安徽师范大学 | Multi-hole nanometer copper oxide composite material, method for preparing same, supercapacitor electrodes and supercapacitor |
| CN103578784A (en) * | 2013-10-16 | 2014-02-12 | 安徽师范大学 | Nanometer copper oxide composite material and preparation method thereof and super-capacitor electrode and super-capacitor |
| CN103578784B (en) * | 2013-10-16 | 2017-02-15 | 安徽师范大学 | Nanometer copper oxide composite material and preparation method thereof and super-capacitor electrode and super-capacitor |
| CN107552069A (en) * | 2017-09-07 | 2018-01-09 | 张家港市汇鼎新材料科技有限公司 | A kind of preparation method of Research of Silver Copper Oxide Composite |
| CN112941556A (en) * | 2021-01-27 | 2021-06-11 | 国家纳米科学中心 | Copper-based solid material and preparation method and application thereof |
| CN112941556B (en) * | 2021-01-27 | 2023-09-15 | 国家纳米科学中心 | Copper-based solid material and preparation method and application thereof |
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