CN113325054B - Fully-integrated portable carbon fiber microelectrode electrochemical sensor and detection system - Google Patents
Fully-integrated portable carbon fiber microelectrode electrochemical sensor and detection system Download PDFInfo
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Abstract
The invention discloses a fully-integrated portable carbon fiber microelectrode electrochemical sensor and a detection system, and belongs to the field of electrochemical sensors. The electrochemical sensor comprises a carbon fiber microelectrode, a connecting component and a substrate electrode; the connecting assembly can be assembled on the substrate electrode, and the carbon fiber microelectrode can be embedded and assembled in the channel to serve as a working electrode; in the assembled state of the three, the bottom opening of the detection pool is attached to the upper surface of the substrate layer to form a container for containing the liquid to be detected; the detection ends of other electrodes except the working electrode in the detection electrode system are all positioned in the container, and the electrode measuring section also extends into the detection cell to jointly form a complete detection electrode system. The electrochemical sensor can be placed into an electrochemical signal adapter for measurement, a portable detection system is formed by the intelligent device, the electrochemical signal adapter and the electrochemical sensor, the simplicity of operation and the carrying convenience are greatly improved, and the electrochemical sensor is applicable to multiple scenes.
Description
Technical Field
The invention belongs to the field of electrochemical sensors, and particularly relates to a fully-integrated portable gold nanoflower modified carbon fiber microelectrode electrochemical sensor.
Background
Electrochemical sensors are often used in the determination of the concentration of a target analyte in a liquid sample and play an important role in the field of analytical chemistry. Electrodes, which are key components of electrochemical sensors, are important factors in determining the performance of the sensors. At present, electrodes can be divided into three categories according to the physical form of their electrochemical interface: the first type is a conventional master electrode, such as a Glassy Carbon Electrode (GCE), a noble metal electrode (e.g., Au, Pt), etc. They have been widely used because of their good stability and repeatability. The second type is the Screen Printed Electrode (SPE), usually in the form of a three-electrode. The screen printing technology makes the preparation of the disposable electrochemical biosensor electrode possible, and the method has simple process and low cost, is suitable for the industrial production of the electrode, and is particularly suitable for daily use. Therefore, the screen printing electrode based on the electrochemical biosensor is widely applied in the field of point-of-care testing (POCT). The third category is some homemade materials developed as self-supporting working electrodes, including 2D/3D carbon-based/metal substrate materials (e.g. graphene foam, MXene, etc.). Their inherent functional surface provides a large sensing surface and good catalytic activity. Although the electrodes described above play an important role in the construction of various sensors, limitations and inherent defects in the manufacturing process have hindered their use. In general, the congenital defect of the disk electrode is mainly caused by the fact that the disk electrode cannot work alone, so that the participation of independent counter electrodes and reference electrodes (CE and RE) is often required. This inevitably leads to bulky sensing equipment and increased sample consumption. Furthermore, the complexity of the three-electrode system increases the risk of operational and systematic errors, negatively affecting the accuracy and precision of the test results. In order to obtain a sensor with high sensitivity and wide response range, most disk-shaped electrodes need to be decorated with functional materials, which sacrifices simplicity and repeatability. In contrast, the integrated three-electrode design of SPE simplifies the sensor setup and miniaturizes the measurement dimensions. However, similar to the disk electrode, the limited sensing area of the SPE still requires further modification. In summary, it is necessary to provide a method for using an electrochemical sensing device, which has a simple structure, is convenient to operate, has a wide sensing area, and is easy for mass production.
The ultramicroelectrode refers to an electrode having a size in the range of μm and/or nanometer, and can exhibit many excellent electrochemical characteristics when the electrode is reduced from millimeter to micrometer. The carbon fiber monofilament has the diameter of only a few micrometers, can be directly prepared into a microelectrode, has high specific strength and Young modulus, good conductivity, high temperature resistance, corrosion resistance and other excellent performances, is prepared into a microelectrode material with good stability and repeatability after clicking, can be suitable for various occasions, and is a microelectrode material which is concerned in recent years. The continuous microcosmic, high sensitivity, high selectivity, miniature, rapid test tool also becomes the necessary product for analysis workers, and the preparation of ultramicro electrode is an important direction for the development of the current electroanalytical chemistry. In the field of electrochemical research, gold electrodes are one of the most commonly used electrodes in electrochemical research and application due to their excellent electrochemical properties and easy modification. By the advantage of gold nanoflower modification of the carbon fiber microelectrode, the effective area and the current reaction of the carbon fiber microelectrode can be increased, and the good stability and reproducibility of the microelectrode are ensured.
The current super microelectrode sensor can detect only by connecting an electrochemical workstation or large equipment. Expensive equipment increases the cost of sensor construction and use and also presents difficulties for practical applications. Meanwhile, the carbon fiber microelectrode often needs to participate in an independent counter electrode and a reference electrode in the detection process, and an integrated electrode system based on the carbon fiber microelectrode is not reported at present. Therefore, the development of a fully integrated portable carbon fiber microelectrode electrochemical sensor is of great significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a fully-integrated portable screen-printed electrochemical sensor based on a carbon fiber microelectrode.
In order to solve the technical problems, the invention adopts the following specific technical scheme:
in a first aspect, the invention provides an electrochemical sensor of a fully integrated portable carbon fiber microelectrode, which comprises a carbon fiber microelectrode, a connecting component and a substrate electrode;
the carbon fiber microelectrode is formed by sequentially connecting an electrode measuring section, an electrode protecting section and an electrode connecting section;
the connecting assembly is a strip-shaped piece which is thick and does not absorb water, a detection pool penetrating through the thickness direction of the strip-shaped piece is formed in the surface of the connecting assembly, a channel and a contact point are also formed in the connecting assembly, the end part of the channel is communicated with the detection pool, and the contact point is in conductive connection with a connection point penetrating through the thickness direction of the strip-shaped piece;
the substrate electrode is printed with other electrodes except the working electrode in the detection electrode system on the substrate layer, and electrode contact points of all the electrodes including the working electrode in the detection electrode system;
the connecting component can be assembled on the substrate electrode, and the carbon fiber microelectrode can be embedded and assembled in the channel to serve as a working electrode; in the assembled state of the three, the bottom opening of the detection pool is attached to the upper surface of the substrate layer to form a container for containing the liquid to be detected; the detection ends of other electrodes except the working electrode in the detection electrode system are all positioned in the container, the electrode measuring section also extends into the detection cell, and the electrode connecting section is electrically connected with the electrode contact point of the working electrode on the basal layer sequentially through the contact point and the connecting point to form a complete detection electrode system.
Preferably, the surface of the carbon fiber microelectrode is modified with gold nanoflowers.
Preferably, the connecting assembly is formed by 3D printing, and the printing material is preferably resin, nylon, silica gel, polycarbonate or ABS.
Preferably, the detection electrode system is a three-electrode system, the substrate layer is printed with a counter electrode and a reference electrode except for the working electrode, and is simultaneously printed with a counter electrode contact point, a working electrode contact point and a reference electrode contact point, and the counter electrode and the reference electrode are respectively in conductive connection with the counter electrode contact point and the reference electrode contact point.
Preferably, the electrode on the base layer is implemented by one or more of a screen printing method, a photolithography method, a wax printing method, an ink-jet method and a drawing method.
Preferably, the electrode on the substrate layer is preferably realized by adopting a screen printing method, and the printing material is carbon paste, Ag/AgCl, graphene-doped carbon paste, carbon nano tube or Prussian blue.
Preferably, the carbon fiber microelectrode comprises a carbon fiber monofilament and a metal wire which are in conductive connection, the carbon fiber monofilament and the metal wire are wrapped in a sealing mode at the outer parts of the capillary glass tube in a homoesthetic mode to form an electrode protection section, one end, extending out of the capillary glass tube, of the carbon fiber monofilament is used as an electrode measurement section, and the other end, extending out of the capillary glass tube, of the metal wire is used as an electrode connection section.
Preferably, the connecting member is fixed to the base electrode by a removable adhesive.
In a second aspect, the invention provides a fully integrated portable carbon fiber microelectrode electrochemical detection system, which comprises a smart device, an electrochemical signal adapter and an electrochemical sensor according to any one of claims 1 to 8; electrode contact points of all electrodes in the electrochemical sensor are connected with corresponding contacts in an electrochemical signal adapter, and the electrochemical signal adapter serves as an electrochemical workstation to process electric signals of all electrodes in the electrochemical sensor; the intelligent device is provided with a communication interface matched with the electrochemical signal adapter, and can acquire the detection signal output by the electrochemical signal adapter and display and/or process and/or transmit data.
Preferably, the intelligent device is an intelligent mobile device, the communication interface is a USB interface, and the electrochemical signal adapter is a USB-type electrochemical workstation.
The integrated portable carbon fiber microelectrode is designed based on the carbon fiber microelectrode and the screen printing electrode, the fusion of the advantages of different electrodes is realized, the detection sensitivity can be effectively improved, and meanwhile, the electrodes can be quickly and conveniently produced in batches, so that the wide application of the integrated portable carbon fiber microelectrode in the field of biochemical analysis is promoted.
The invention has the following advantages:
1. according to the invention, the screen-printed electrode and the carbon fiber microelectrode are fused, so that the integrated carbon fiber microelectrode system electrochemical sensor suitable for portable detection can be obtained, the advantages of the microelectrode are effectively utilized, meanwhile, the screen-printed electrode meets the requirement of rapid preparation and batch production, and in addition, a detection pool in the connecting component can be used for detection and incubation of a solution in the measurement process.
2. The connecting assembly can be fixed on the substrate electrode in an adhesion mode, after detection is finished, the connecting assembly can be taken down from the substrate electrode again to remove glue on the substrate electrode, and the carbon fiber microelectrode is detached, so that the connecting assembly can be used as a reaction container of the electrode for repeated use, the use cost is greatly reduced in practical application, materials are saved, the cost is reduced, and repeated tests can be carried out only by replacing the working electrode.
3. The invention can further select carbon fibers with good electrochemical performance as a substrate, decorate the gold nanoflowers on the surface of the carbon fibers, enable the carbon fibers to have better conductivity and larger specific surface area, can be used as a working electrode for electrochemical detection, have stable electrochemical performance, and can be effectively used for target biomolecule analysis.
4. The portable detection system is formed by the intelligent equipment, the electrochemical signal adapter and the electrochemical sensor, so that the simplicity of operation and the convenience of carrying are greatly improved, and the portable detection system has multiple application scenes.
Drawings
FIG. 1 is a schematic structural diagram of an electrochemical detection system according to the present invention in a use state.
FIG. 2 is a schematic view showing the structure of a carbon fiber microelectrode of the present invention;
FIG. 3 is a schematic top view of a connecting assembly of the present invention
FIG. 4 is a schematic front view of a connecting assembly according to the present invention
FIG. 5 is a schematic cross-sectional view of the middle channel of the connecting assembly of the present invention
FIG. 6 is a schematic top view of the electrode substrate of the present invention
FIG. 7 is an electron microscope scan of the gold nanoflower carbon fiber microelectrode of the present invention, wherein A is an EDS image of an unmodified carbon fiber microelectrode, B is a gold nanoflower modified carbon fiber microelectrode, and C is a carbon fiber microelectrode.
FIG. 8 is a CV scan of the gold nanoflower carbon fiber microelectrodes of the present invention
In the figure: the electrochemical detection device comprises a smart phone 1, an electrochemical signal adapter 2, an electrochemical sensor 3, a communication interface 21, an indication mark 22, a detection component interface 23, a carbon fiber microelectrode 31, a connection component 32, a substrate electrode 33, an electrode measurement section 311, an electrode protection section 312, an electrode connection section 313, a detection cell 321, a channel 322, a contact point 323, a detection cell bottom surface 324, a reserved part 325, a connection point 326, a detection cell side wall 327, a channel top surface 328, an electrode substrate 331, a counter electrode contact point 332, a working electrode contact point 333, a reference electrode contact point 334, a counter electrode 335, a reference electrode 336 and a detection cell position area 337.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
In a preferred embodiment of the present invention, as shown in fig. 1, there is provided a fully integrated portable carbon fiber microelectrode electrochemical detection system, whose main components include three parts, namely, a smart device 1, an electrochemical signal adapter 2 and an electrochemical sensor 3.
The intelligent device 1 has an independent operating system and an independent operating space, can be used for a user to install program software provided by a third-party service provider, and can realize wireless network access through a mobile communication network, and is commonly a mobile device such as a smart phone, a Pad and the like or a portable computer.
In addition, the electrochemical signal adapter 2 functions as an electrochemical workstation, can process the electric signal of the electrochemical sensor 3, and should meet the requirements of miniaturization and convenience. In this embodiment, a U-disk electrochemical workstation, such as a PalmSens U-disk electrochemical workstation, may be used. The intelligent device 1 can be provided with a USB interface to communicate with the electrochemical signal adapter 2.
In addition, the core of the electrochemical detection system in the invention is an electrochemical sensor 3, the electrochemical sensor 3 is an integrated detection electrode system integrating a substrate electrode and a carbon fiber microelectrode, electrode contact points of each electrode in the detection electrode system are all connected with corresponding contact points in an electrochemical signal adapter 2, and the electrochemical signal adapter 2 is used as an electrochemical workstation to process electric signals of each electrode in the electrochemical sensor 3. The intelligent device 1 is provided with a communication interface matched with the electrochemical signal adapter 2, the electrochemical signal adapter 2 and the intelligent device 1 form data transmission through the communication interface, therefore, the intelligent device 1 can obtain a detection signal output by the electrochemical signal adapter 2 through the software degree in the intelligent device 1 and realize a data function according to needs, and the specific data function comprises but is not limited to data display, data post-processing and data remote transmission and can be combined according to user requirements.
Referring to fig. 1, the electrochemical sensor 3 of the present invention is composed of three parts, namely, a carbon fiber microelectrode 31, a connecting component 32 and a substrate electrode 33.
As shown in FIG. 2, the carbon fiber microelectrode 31 has a three-stage structure and is formed by connecting an electrode measuring section 311, an electrode protecting section 312 and an electrode connecting section 313 in this order. The electrode measuring section 311 is a detection end of the whole electrode for contacting with a liquid to be detected to generate an oxidation-reduction reaction, the electrode protecting section 312 is a part with a protective shell on a bare electrode, and the electrode connecting section 313 is a part for directly or indirectly connecting with an external circuit contact. The specific material and processing technique of the three-stage structure of the carbon fiber microelectrode 31 can be adjusted according to actual conditions.
In the embodiment, the carbon fiber microelectrode 31 comprises a carbon fiber monofilament and a metal wire which are electrically connected, and the carbon fiber monofilament and the metal wire are externally sealed and wrapped with capillary glass tubes to form an electrode protection section 312, one end of the carbon fiber monofilament extending out of the capillary glass tubes is used as an electrode measuring section 311, and the other end of the metal wire extending out of the capillary glass tubes is used as an electrode connecting section 313. The metal wire may be any conductive metal, preferably copper in this embodiment. The manufacturing process of the carbon fiber microelectrode 31 is as follows: one end of the carbon fiber monofilament is connected with one end of the copper wire through the conductive adhesive, then the other end of the copper wire penetrates through the capillary glass tube and drives the carbon fiber monofilament to gradually enter until the joint of the carbon fiber monofilament and the copper wire is completely arranged in the capillary tube, then the two ends of the capillary tube are sealed by using epoxy resin, and the carbon fiber monofilament and the copper wire are respectively kept to be positioned outside the capillary glass tube. Generally speaking, the exposed length of the carbon fiber monofilament can be controlled within the range of 10mm to 400mm, the exposed length of the copper conductor can be controlled within the range of 1cm to 3cm, and the diameter of the carbon fiber monofilament can be controlled within the range of 5 μm to 10 μm. . Further, the conductive adhesive is preferably conductive silver paste, and the epoxy resin is preferably fast-curing epoxy resin.
As shown in fig. 3, the connecting member 32 is a strip having a thickness and not absorbing water, i.e., it has a rectangular parallelepiped shape as a whole. The surface of the connecting component 32 is provided with a detection cell 321, and the connecting component 32 is also provided with a channel 322 and a contact point 323. The detection cell 321 and the contact point 323 are respectively located on two sides of the channel 322, and the channel 322 is opened along the length direction of the strip. One end of the channel 322 communicates with the detection cell 321, and the contact point 323 is provided at the other end. It should be noted that, referring to fig. 4 and 5, the cuvette 321 needs to penetrate through the whole strip in the thickness direction but cannot penetrate through the side wall of the strip in the lateral direction, i.e. the cuvette bottom 324 is directly perforated, and the cuvette side wall 327 needs to keep a certain distance from the side wall of the strip. But the channel 322 should not extend through the entire thickness of the strip, i.e., there should still be a thickness of the remaining portion 325 below the bottom of the channel 322, but the channel top surface 328 needs to be flush with the strip top surface. However, the height of the channel 322 itself should not be too small, and should be able to accommodate the electrode protection section 312 of the lower carbon fiber micro-electrode 31 so that the carbon fiber micro-electrode 31 can be embedded therein. The contact point 323 at the end of the channel 322 functions to overlap the electrode connection section 313 of the carbon fiber microelectrode 31, introducing an electrical signal to the corresponding electrode contact point on the underlying substrate electrode 33. However, the contact 323 is only located on the bottom surface of the trench 322, and therefore, it is also necessary to provide a connection point 326 on the aforementioned remaining portion 325, the connection point 326 penetrating the thickness direction of the bar, so that the contact 323 can be electrically connected to the corresponding electrode contact on the underlying substrate electrode 33 via the connection point 326.
The connecting component 32 in the invention can be printed by a 3D printer, the precision can be set to be 0.1mm, and the selected material can be made of materials supporting 3D printing, such as transparent resin, nylon, silica gel, polycarbonate PC, ABS and the like.
In the present invention, the carbon fiber microelectrodes 31 mounted in the connection module 32 are used as replaceable working electrodes in the whole detection electrode system, while other electrodes required for constituting the whole detection electrode system are printed on the substrate electrode 33. The detection electrode system in the present invention may be a two-electrode system or a three-electrode system. If the detection electrode system is a two-electrode system, a counter electrode needs to be printed on the base electrode 33, and if the detection electrode system is a three-electrode system, a counter electrode and a reference electrode need to be printed on the base electrode 33. The base electrode 33 is mainly formed of the base layer 331, and the material thereof is not limited to PVC, PET, or the like.
As shown in fig. 6, the detection electrode system in this embodiment is a three-electrode system, and therefore the base layer 331 is printed with the counter electrode 335 and the reference electrode 336 of the detection electrode system, excluding the working electrode. Meanwhile, since each electrode needs to be connected to an external circuit through an electrode contact point, electrode contact points of all electrodes including the working electrode in the detection electrode system, namely, a counter electrode contact point 332, a working electrode contact point 333 and a reference electrode contact point 334 are printed on the base layer 331, the counter electrode 335 and the reference electrode 336 are respectively in conductive connection with the counter electrode contact point 332 and the reference electrode contact point 334, and the working electrode contact point 333 is connected to the working electrode when in use. Therefore, the electrochemical signal adapter 2 comprises a communication interface 21 which can be connected with the intelligent device 1, a detection component interface 23 which can be connected with a three-electrode system, and an indication mark 22 of the device state is displayed on the adapter, and the indication mark 22 can be realized by a signal lamp. The detection component interface 23 of the three-electrode system in the electrochemical signal adapter is matched with the size of the portable carbon fiber microelectrode 31.
In the present invention, the electrode on the base layer 331 can be implemented by one or more of screen printing, photolithography, wax printing, ink-jet printing, and drawing, and the screen printing is preferably used in this embodiment. The material of the printing electrode can be carbon paste, Ag/AgCl, graphene-doped carbon paste, carbon nano-tubes or Prussian blue. In this embodiment, the counter electrode 335 is a carbon paste layer and the reference electrode 336 is a silver chloride layer. In addition, carbon paste, gold paste, silver paste, or the like is used for the counter electrode contact 332, the working electrode contact 333, and the reference electrode contact 334.
In the electrochemical sensor 3 of the present invention, the carbon fiber micro-electrode 31, the connection member 32 and the base electrode 33 are detachably combined. Wherein, the connecting component 32 can be fixed on the upper surface of the basal layer 331 by removable adhesive, and the carbon fiber microelectrode 31 is embedded in the channel 322 as the working electrode. In an assembled state, the bottom opening of the detection cell 321 is attached to the upper surface of the substrate layer 331 to form a container for containing the liquid to be detected, and the other positions of the container except the top opening are sealed and waterproof, so that the container can be used as a container for dripping and storing the liquid to be detected, and can also be used as a container for incubation, cleaning and other operation steps according to the requirements of a detection process. When detection is carried out, the detection ends of the counter electrode 335 and the reference electrode 336 except the working electrode in the detection electrode system are positioned in the container and can be contacted with liquid to be detected. Meanwhile, the electrode measuring section 311 as a working electrode also extends into the detection cell 321 through the channel 322. The electrode connecting section 313 of the working electrode is electrically connected with the electrode contact point of the working electrode on the base layer 331 through the contact point 323 and the connection point 326 in turn, so that the working electrode, the counter electrode 335 and the reference electrode 336 form a complete three-electrode detection system.
Therefore, in order to facilitate the alignment of the connection component 32 and the base electrode 33 during the assembly, a detection cell position region 337 may be marked on the base layer 331 in advance, the detection cell position region 337 should cover the detection ends of the counter electrode 335 and the reference electrode 336, and then the connection component 32 may be directly aligned and mounted according to the detection cell position region 337.
The connecting member 32 may be bonded to the base electrode 33 by glue, and the bonding material may be an adhesive such as epoxy resin. After the detection is finished, the connecting component 32 can be taken down from the substrate electrode 33 again to remove the glue thereon, and the carbon fiber microelectrode 31 is detached, so that the connecting component 32 can be reused.
Of course, it should be noted that the carbon fiber microelectrode 31 is not necessarily paired with the smart device 1 or the electrochemical signal adapter 2, and may be used alone for detection in other scenes.
In another preferred embodiment of the present invention, gold nanoflower modification can be performed on the carbon fiber monofilament in the carbon fiber microelectrode 31 on the basis of the carbon fiber microelectrode 31. The gold nanoflowers on the surface of the carbon fiber microelectrode 31 can be modified by an electroplating process, the surface of the activated carbon fiber is electroplated to deposit gold nanoflowers, and the gold nanoflowers with different shapes, quantities and sizes can be obtained by controlling the voltage and the electroplating time.
In order to show the difference between the bare carbon fiber microelectrode which is not decorated by the gold nanoflowers and the carbon fiber microelectrode which is decorated by the gold nanoflowers, the corresponding comparison test is arranged below.
As shown in FIG. 7, Panel A is an unmodified carbon fiber microelectrode, 7 μm in diameter. Constant pressure at 1mM HAuCl by 0V4/0.1M KNO3The solution is electroplated for 50 seconds, the gold nano-flower particles are uniformly plated on the surface of the electrode, and the gold nano-flower particles can be seen in the enlarged view, and the gold nano-flower particles have larger surface area due to flower shape, so that the electrochemical performance of the electrode can be improved.
The two electrodes are tested by an IVIUM electrochemical workstation, the prepared carbon fiber microelectrode modified by the gold nanoflowers is subjected to electrochemical activity characterization by electrochemical Cyclic Voltammetry (CV), a three-electrode system is adopted, namely platinum wires are used as counter electrodes, a standard Ag/AgCl electrode is used as a reference electrode, a scanning potential window is 0-0.6V, the scanning speed is 10mV/s, and a test solution is 2.5mM [ Fe (CN)6]]3+/[Fe(CN)6]4+(1:1) (containing 0.1M KCl). Fig. 8 is a schematic view of a cyclic voltammetry curve of the gold nanoflower modified carbon fiber microelectrode of the present invention, and compared with a bare carbon fiber electrode, the current of the carbon fiber electrode modified by gold nanoflowers is significantly increased, so that a standard "S" type microelectrode voltammetry characteristic curve can be obtained, which indicates that the gold nanoflower modified carbon fiber microelectrode has good electrochemical performance.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. For example, connector 32 may be used in an alternative configuration to connect the working electrode to the counter electrode to the reference electrode to form a three-electrode system. In addition, the measuring electrode system can also be used as a two-electrode system if necessary. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (9)
1. A fully integrated portable carbon fiber microelectrode electrochemical sensor, characterized in that the electrochemical sensor (3) comprises a carbon fiber microelectrode (31), a connection component (32) and a substrate electrode (33);
the carbon fiber microelectrode (31) is formed by sequentially connecting an electrode measuring section (311), an electrode protecting section (312) and an electrode connecting section (313);
the connecting assembly (32) is a strip-shaped member which is thick and does not absorb water, a detection pool (321) penetrating through the thickness direction of the strip-shaped member is formed in the surface of the connecting assembly (32), a channel (322) and a contact point (323) are also arranged on the connecting assembly (32), the end part of the channel (322) is communicated with the detection pool (321), and the contact point (323) is in conductive connection with a connection point (326) penetrating through the thickness direction of the strip-shaped member;
the substrate electrode (33) is printed with other electrodes except the working electrode in the detection electrode system on the substrate layer (331), and electrode contact points of all the electrodes including the working electrode in the detection electrode system;
the connecting component (32) can be assembled on the substrate electrode (33), and the carbon fiber microelectrode (31) can be embedded and assembled in the channel (322) to be used as a working electrode; in the assembled state of the three, the bottom opening of the detection cell (321) is attached to the upper surface of the substrate layer (331) to form a container for containing the liquid to be detected; the detection ends of other electrodes except the working electrode in the detection electrode system are positioned in the container, the electrode measuring section (311) also extends into the detection cell (321), and the electrode connecting section (313) is electrically connected with the electrode contact point of the working electrode on the substrate layer (331) through a contact point (323) and a connection point (326) in sequence to form a complete detection electrode system;
the carbon fiber microelectrode (31) comprises a carbon fiber monofilament and a metal wire which are in conductive connection, the carbon fiber monofilament and the metal wire are simultaneously sealed and wrapped outside the capillary glass tube to form an electrode protection section (312), one end of the carbon fiber monofilament, which extends out of the capillary glass tube, serves as an electrode measurement section (311), and the other end of the metal wire, which extends out of the capillary glass tube, serves as an electrode connection section (313).
2. The fully integrated portable carbon fiber microelectrode electrochemical sensor of claim 1, wherein the carbon fiber microelectrode (31) is decorated with gold nanoflowers on its surface.
3. The fully integrated portable carbon fiber microelectrode electrochemical sensor of claim 1, wherein the connection assembly (32) is 3D printed with a printing material of resin, nylon or silicone.
4. The fully integrated portable carbon fiber microelectrode electrochemical sensor of claim 1, wherein the detection electrode system is a three-electrode system, the substrate layer (331) is printed with a counter electrode (335) and a reference electrode (336) in addition to the working electrode, and is simultaneously printed with a counter electrode contact point (332), a working electrode contact point (333), and a reference electrode contact point (334), and the counter electrode (335) and the reference electrode (336) are respectively connected with the counter electrode contact point (332) and the reference electrode contact point (334) in an electrically conductive manner.
5. The fully integrated portable carbon fiber microelectrode electrochemical sensor of claim 1, wherein the electrodes on the substrate layer (331) are implemented using one or more of screen printing, photolithography, wax printing, ink-jet, drawing.
6. The fully integrated portable carbon fiber microelectrode electrochemical sensor of claim 1, wherein the electrodes on the substrate layer (331) are realized by screen printing, and the printing material is carbon paste, Ag/AgCl, graphene-doped carbon paste, carbon nanotubes or prussian blue.
7. The fully integrated portable carbon fiber microelectrode electrochemical sensor of claim 1, characterized in that the connection component (32) is fixed to the base electrode (33) by a removable adhesive.
8. An electrochemical detection system of a fully integrated portable carbon fiber microelectrode, which is characterized by comprising an intelligent device (1), an electrochemical signal adapter (2) and an electrochemical sensor (3) according to any one of claims 1 to 7; electrode contact points of all electrodes in the electrochemical sensor (3) are connected with corresponding contact points in the electrochemical signal adapter (2), and the electrochemical signal adapter (2) serves as an electrochemical workstation to process electric signals of all electrodes in the electrochemical sensor (3); the intelligent device (1) is provided with a communication interface matched with the electrochemical signal adapter (2), and can acquire a detection signal output by the electrochemical signal adapter (2) and display and/or process and/or transmit data.
9. The electrochemical detection system of the fully integrated portable carbon fiber microelectrode of claim 8 is characterized in that the intelligent device (1) is an intelligent mobile device, the communication interface is a USB interface, and the electrochemical signal adapter (2) is a USB-type electrochemical workstation.
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