CN117110392A - Electrochemical sensor based on copper-based multi-metal microelectrode and preparation method and application method thereof - Google Patents
Electrochemical sensor based on copper-based multi-metal microelectrode and preparation method and application method thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 59
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 37
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- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010931 gold Substances 0.000 claims abstract description 72
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052737 gold Inorganic materials 0.000 claims abstract description 46
- 239000002105 nanoparticle Substances 0.000 claims abstract description 44
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 20
- 239000008103 glucose Substances 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 11
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 229910001020 Au alloy Inorganic materials 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- 229910018883 Pt—Cu Inorganic materials 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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Abstract
The invention provides an electrochemical sensor based on a copper-based multi-metal microelectrode, and a preparation method and an application method thereof. The electrochemical sensor is a three-electrode system sensor, the counter electrode is a platinum wire electrode, the reference electrode is a saturated calomel electrode, and the working electrode of the copper-based multi-metal microelectrode electrochemical sensor is a copper microelectrode; the surface of the copper microelectrode is provided with gold nanoparticles prepared by an electrochemical method in one step. The preparation of the working electrode comprises the following steps: selecting or preparing copper microelectrodes; a three-electrode system is adopted, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a copper microelectrode is used as a working electrode, and gold nanoparticles are deposited on the surface of the copper microelectrode by an electrochemical method. The invention constructs a bimetal electrode for electrochemical detection and sensing, which takes a cylindrical copper microelectrode as a matrix and nano gold as a modifier. The micrometer electrode with the micro-nano structure on the surface is directly prepared by a local electrochemical method, and the micrometer electrode has a large active area and can increase the active site of the electrode to react with glucose.
Description
Technical Field
The invention belongs to the technical field of electrochemical sensors, and particularly relates to a microelectrode sensor with a multi-metal catalytic electrode, a preparation method and an application method thereof.
Background
The electrochemical sensor with metal as the working electrode to construct a three-electrode system is an important research direction for detecting small molecular substances without enzyme catalysis; this method has been widely used in the field of substance content analysis and detection. The basic principle of the detection method is that metal has a catalytic effect on certain small molecular substances under the action of an electric current field. Thus, some metals have been developed as working electrodes for the catalytic detection of methanol, ethanol, acetic acid, and glucose. However, most of the conventional working electrode materials are noble metals, and the preparation process is complex and the cost is high. And the conventional single noble metal is adopted as a working electrode, so that the problem of insufficient catalytic capability can be caused, and the detection limit of the finally prepared electrochemical sensor is insufficient.
Therefore, researchers can improve the electrode catalytic performance by developing the multi-metal electrode, and solve the problems of insufficient electrode catalytic efficiency, high preparation cost of the noble metal electrode and the like. The more common way is to use noble metals in combination with other transition metals such as copper. However, the nano-material multi-metal catalytic electrode prepared by the prior art is mostly prepared by firstly synthesizing a metal nano-material and then coating the metal nano-material on the surface of a large electrode (millimeter scale). For example, in the patent CN102636536b—preparation and application of Pt-Cu alloy hollow nanoparticle enzyme-free glucose sensor electrode, a metal nanomaterial is prepared first, and then chitosan is used as a binder, and a chitosan-metal nanomaterial mixture is coated on the surface of the gold electrode. The metal nano material is synthesized by a chemical method, and then is modified to the surface of a large electrode (millimeter scale) or printed/printed to prepare electrochemical sensing for a microelectrode, the problems of active site loss, poor stability of electrode modification, poor detection parallelism and the like in the transfer process of the nano material are possibly caused, and the combination among various metals is not firm enough, and the problems of weak conductivity, easy falling and the like are caused. In addition, the preparation process is complicated because special steps are needed to prepare the metal nano material in the preparation process. Therefore, there is a need to further develop a multi-metal catalytic electrode electrochemical sensor which is free of nanomaterial modification, can be prepared in situ, and is simple to operate.
Disclosure of Invention
The invention aims at solving the technical problems in the background technology and provides an electrochemical sensor based on a copper-based multi-metal microelectrode, and a preparation method and an application method thereof.
The scheme provided by the invention is as follows:
an electrochemical sensor based on a copper-based metal microelectrode is a three-electrode system sensor, a counter electrode is a platinum wire electrode, a reference electrode is a saturated calomel electrode, and a working electrode of the copper-based metal microelectrode electrochemical sensor is a copper microelectrode; the surface of the copper microelectrode is provided with gold nanoparticles prepared by an electrochemical method in one step.
The preparation of the bimetallic nano-particles can obviously improve the electron distribution and the three-dimensional morphology of the surface of the working electrode, which is beneficial to improving the sensing performance. By combining three-dimensional transition metals (Cu, fe) and noble metals, the electrode catalytic activity can be greatly improved. The bimetallic catalytic electrode taking the transition metal as a main component and the noble metal as an auxiliary component not only shows excellent catalytic performance, but also greatly reduces the preparation cost of the noble metal electrode.
As a preferable mode of the technical scheme, the crystal face quantity ratio of the gold nanoparticles deposited on the surface of the copper microelectrode is Au (200): au (111) is greater than 1:2. In the range of the crystal face quantity proportion, the obtained working electrode has better coverage of detection limit, tolerance and catalytic performance.
Based on the same technical conception, the invention also provides a method for preparing the electrochemical sensor based on the copper-based multi-metal microelectrode, wherein the copper-based multi-metal microelectrode electrochemical sensor is a three-electrode system sensor, a counter electrode is a platinum wire electrode, a reference electrode is a saturated calomel electrode, and the preparation of a working electrode comprises the following steps:
(1) Copper microelectrodes are selected or prepared.
(2) A three-electrode system is adopted, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a copper microelectrode is used as a working electrode, and gold nanoparticles are deposited on the surface of the copper microelectrode by an electrochemical method.
As the optimization of the technical scheme, when the gold nanoparticles are electrochemically deposited, the ratio of Au (200) crystal faces in the growth process of the gold nanoparticles is adjusted by adjusting the current intensity. The crystal face energy is taken as an important factor affecting the catalytic efficiency, and the traditional crystal face regulation is realized based on temperature regulation in the hydrothermal synthesis process, reaction speed regulation and the selective action of the end capping reagent. The invention creatively regulates and controls the crystal face composition of gold nano-particles exposed by electrochemical in-situ growth dynamics, thereby regulating the catalytic capability and the antitoxic capability of the gold nano-particles to glucose.
As a preferable aspect of the above technical solution, the Au (200) crystal plane ratio is increased by decreasing the growth current intensity of the gold nanoparticles when the gold nanoparticles are electrochemically deposited.
As the optimization of the technical scheme, when the electrochemical deposition of the gold nanoparticles is carried out, the Au (200) crystal face proportion in the growth process of the gold nanoparticles is regulated by changing the working mode of the electrode when the current intensity is unchanged; when the current intensity is unchanged, the working current is converted from direct current to pulse current so as to increase the Au (200) crystal face proportion of the gold nanoparticles.
As the optimization of the technical scheme, the preparation of the copper microelectrode is that the cathode is fixed in an electrolytic tank, the anode is arranged in an electrochemical deposition three-dimensional moving platform, and the distance between the cathode and the anode and the potential difference are regulated and controlled by a control system, so that the directional growth of the copper microelectrode on the cathode is realized. Compared with the copper microelectrode obtained by the conventional photoetching method, the copper microelectrode prepared by the method has the micro-nano structure on the surface, and the active site of electrode catalysis can be greatly increased.
As a preferable mode of the technical scheme, the electrolyte solution adopted by the three-electrode system comprises chloroauric acid solution with the concentration of 0.1g/L-10 g/L.
As a preferable mode of the technical scheme, the deposition voltage of the electrochemical deposition is-0.5V to 0.7V, and the deposition time is 10s-200s.
Based on the same technical conception, the invention also provides an application method of the electrochemical sensor based on the copper-based multi-metal microelectrode, wherein the electrochemical sensor is used for detecting glucose by a cyclic voltammetry or a chronoamperometry, and the detection environment is alkaline.
Compared with the prior art, the invention has the beneficial effects that:
the invention constructs a bimetal electrode for electrochemical detection and sensing, which takes a cylindrical copper microelectrode as a matrix and nano gold as a modifier, and can be used for detecting glucose, wherein the linear detection range is 10 mu M-400000 mu M, and the lowest detection limit is 282nM. The electrode can be stored for a long period at 0deg.C.
The invention directly prepares the micrometer-scale electrode with the micro-nano structure on the surface by a local electrochemical method, and the preparation is carried out by a one-step method, so that the steps of nanocrystallization modification are omitted, and the steps of conventional material synthesis, electrode coating and the like are omitted; the micro-nano structure and the electrode body prepared by the one-step method are integrated, and the stability is good. The electrode with the microstructure on the surface greatly increases the active area of the electrode, the active area of the electrode is tens of times of the geometric area, and for substances which are dynamically controlled in the oxidation process of improving glucose, the large active area can effectively increase the active site of the electrode for reacting with glucose.
The invention provides a novel method for regulating and controlling the crystal face proportion of gold nanoparticles; the Au (200) crystal face proportion in the gold nanoparticle growth process is adjusted by adjusting the current intensity, and the Au (200) crystal face proportion in the gold nanoparticle growth process is adjusted by changing the working mode of the electrode when the current intensity is unchanged. The preparation and regulation are in situ, so the operation is simple and controllable.
Drawings
FIG. 1 is an SEM and SEM-EDS diagram of a copper microelectrode prepared according to example 1 of the present disclosure (where FIG. 1 (a) is an SEM diagram and FIGS. 1 (b) and 1 (c) are SEM-EDS diagrams);
FIG. 2 is a graph showing CV curves of copper microelectrodes without gold nanoparticles deposited in example 1 at different scanning rates in NaOH solution;
FIG. 3 is a graph of the linear relationship between the corresponding current and scan speed at potential C (-0.35V) in FIG. 2;
FIG. 4 is a graph of the results of a test for the performance of a Cu-Au electrode on glucose (wherein the left graph is a chronoamperometric graph of glucose at different concentrations, and the right graph is a graph of the correlation between the electrode response current to glucose and the glucose concentration);
FIG. 5 is a graph showing the contrast of CV signal intensities of Cu electrodes and Cu-Au bimetallic electrodes;
FIG. 6 is a graph of glucose concentration versus current intensity for different gold nanoparticle growth times;
FIG. 7 is a graph showing the detection of gold nanoparticles prepared in example 1 of the present invention (wherein a: TEM diffraction analysis of electrochemically prepared gold nanoparticles; b: crystal plane diffraction intensity analysis).
Detailed Description
The present invention will be described more fully hereinafter for the purpose of facilitating understanding of the present invention, but the scope of protection of the present invention is not limited to the following specific examples.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
The preparation method of the electrochemical sensor based on the copper-based multi-metal microelectrode comprises the steps that the copper-based multi-metal microelectrode electrochemical sensor is a three-electrode system sensor, a counter electrode is a platinum wire electrode, a reference electrode is a saturated calomel electrode, and a working electrode of the copper-based multi-metal microelectrode electrochemical sensor is a copper microelectrode; the preparation of the copper microelectrode comprises the following steps:
(1) Preparing a copper microelectrode: the electrochemical deposition working platform is adopted, silver sheets are used as cathodes, the cathodes are fixed in the electrolytic tank, anodes are arranged in the three-dimensional moving platform, and the distance between the cathodes and the anodes and the potential difference are regulated and controlled by a control system of the electrochemical deposition working platform, so that the directional growth of the copper microelectrodes is realized.
(2) Depositing gold nanoparticles on the surface of a copper microelectrode by adopting an electrochemical method: the workstation is a Chen Hua electrochemical work Chi660e, a three-electrode system is adopted, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a copper microelectrode is used as a working electrode, chloroauric acid with the concentration of 1g/L is used as a working electrode, and 0.1M KNO is used as a working electrode 3 And using 25mM CTAB solution as electrolyte solution, and depositing gold nano particles on the surface of the copper microelectrode by an electrochemical method to obtain the Cu-Au electrode. The electrochemical method is constant current method, the deposition voltage is-0.5V to 0.7V, the deposition time is 50s, and the deposition current is PC 10 -5 A。
As shown in FIG. 1, the prepared copper microelectrode is obtained by insulating the microelectrode substrate with resin, packaging the resin, and then forming the copper microelectrode with a height of 100 μm and a diameter of 50 μm, wherein the electrode material composition is Cu-Au alloy as shown by SEM-EDS test results. The crystal face condition of the gold nano particles on the prepared Cu-Au electrode is detected, and the result shows that Au (200): au (111) =93:100. The active area of the copper microelectrode which is not deposited with gold nanoparticles is calculated by adopting an electric double layer capacitance method, and the geometric area of the copper cylinder microelectrode used in the experiment is 1.46E-4cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The results are shown in fig. 2 and 3. As can be seen from the slope of the fit of FIG. 3, the electrode double layer capacitance was 4.783E-4mF, with a smooth oxide electrode specific capacitance of 60. Mu.F cm -2 For reference specific capacitance, the electrode active area is 7.97E-3cm 2 The active area is 54.74 times the electrode geometry area. The micro-nano structure of the copper microelectrode surface designed and prepared by the invention can greatly increase the active site of electrode catalytic glucose.
And testing the detection performance of the prepared Cu-Au electrode on glucose. The test method is a chronoamperometry, and the detection environment is alkaline (0.1M NaOH); the test results are shown in fig. 4, using a two-electrode system with a copper microelectrode as the working electrode and a platinum wire as the counter electrode and reference electrode. FIG. 4 shows that the linear detection range is 10. Mu.M-400000. Mu.M with a minimum detection limit of 282nM.
Relevant comparative test of working electrode:
in this example, CV signal intensity comparison tests were performed on Cu electrodes and Cu-Au bimetallic electrodes, i.e., CV signal intensity tests were performed on conventional Cu microelectrodes and Cu-Au bimetallic electrodes prepared in accordance with the present invention, respectively. The CV test solution was composed of 1mM glucose, 0.1M NaOH, and the test was conducted using a three-electrode system with a platinum wire as a counter electrode, a saturated calomel electrode as a reference electrode, and a copper microelectrode as a working electrode, the results of which are shown in FIG. 5. The results in FIG. 5 show that the current signal intensity of the Cu-Au bimetallic electrode is far greater than that of the Cu single metal electrode.
In this embodiment, there is a comparative experiment of the influence of gold nanoparticles with different deposition and growth times on the detection performance, that is, deposition times of 10s, 40s, 70s, and 100s are respectively used to deposit gold nanoparticles, and the prepared electrodes are respectively used for detecting glucose by CV method. The detection results are shown in FIG. 6. FIG. 6 shows the signal of glucose detection by preparing Cu-Au electrodes under different gold nanoparticle growth times, and the result shows that the response of the Cu-Au electrodes to glucose concentration is the most sensitive when the gold deposition time is 40 s.
In this embodiment, an electrochemical parameter adjustment comparison test is performed in the gold nanoparticle modification process, that is, other parameters are unchanged, and only the current intensity or the working mode (direct current and pulse current) is changed, and the comparison result is shown in fig. 7. As can be seen from fig. 7 (b), the Au (200) crystal plane ratio increases by decreasing the gold nanoparticle growth current intensity; under the same current intensity, the Au (200) crystal face ratio of the gold nano-particles prepared by the pulse method is higher than that of the Au (200) crystal face ratio of the gold nano-particles prepared by the direct current method.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall fall within the scope of the technical solution of the present invention.
Claims (10)
1. An electrochemical sensor based on a copper-based metal microelectrode, wherein the electrochemical sensor of the copper-based metal microelectrode is a three-electrode system sensor, a counter electrode of the electrochemical sensor is a platinum wire electrode, and a reference electrode of the electrochemical sensor is a saturated calomel electrode; the surface of the copper microelectrode is provided with gold nanoparticles prepared by an electrochemical method in one step.
2. The electrochemical sensor of claim 1, wherein the ratio of the number of crystal planes in the gold nanoparticles deposited on the surface of the copper microelectrode is Au (200): au (111) is greater than 1:2.
3. A method of making the copper-based multi-metal microelectrode-based electrochemical sensor of claim 1 or 2, which is a three-electrode system sensor whose counter electrode is a platinum wire electrode and reference electrode is a saturated calomel electrode, characterized in that the preparation of the working electrode comprises the steps of:
(1) Selecting or preparing copper microelectrodes;
(2) A three-electrode system is adopted, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a copper microelectrode is used as a working electrode, and gold nanoparticles are deposited on the surface of the copper microelectrode by an electrochemical method.
4. A method according to claim 3, characterized in that the Au (200) crystal plane ratio during the growth of gold nanoparticles is adjusted by adjusting the current intensity when electrochemically depositing gold nanoparticles.
5. The method according to claim 4, wherein the Au (200) crystal plane ratio is increased by decreasing the gold nanoparticle growth current intensity when electrochemically depositing gold nanoparticles.
6. A method according to claim 3, wherein the ratio of Au (200) crystal planes in the growth process of the gold nanoparticles is adjusted by changing the operation mode of the electrode when the current intensity is unchanged when the gold nanoparticles are electrochemically deposited; when the current intensity is unchanged, the working current is converted from direct current to pulse current so as to increase the Au (200) crystal face proportion of the gold nanoparticles.
7. The method according to claim 3, wherein the preparation of the copper microelectrode is to fix the cathode in an electrolytic tank, install the anode in an electrochemical deposition three-dimensional moving platform, and adjust and control the distance between the cathode and the anode and the potential difference by a control system to realize the directional growth of the copper microelectrode on the cathode.
8. The method of any one of claims 3-7, wherein the electrolyte solution employed in the three electrode system comprises chloroauric acid solution at a concentration of 0.1g/L to 10 g/L.
9. The method of claim 8, wherein the electrochemical deposition has a deposition voltage of-0.5V to 0.7V and a deposition time of 10s to 200s.
10. A method for the application of an electrochemical sensor based on a copper-based multi-metal microelectrode according to claim 1 or 2, characterized in that the electrochemical sensor is used for detecting glucose by cyclic voltammetry or chronoamperometry, and the detection environment is alkaline.
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