CN116818875A - Electrochemical sensing device based on vertical graphene microelectrode array and preparation method thereof - Google Patents
Electrochemical sensing device based on vertical graphene microelectrode array and preparation method thereof Download PDFInfo
- Publication number
- CN116818875A CN116818875A CN202310725515.7A CN202310725515A CN116818875A CN 116818875 A CN116818875 A CN 116818875A CN 202310725515 A CN202310725515 A CN 202310725515A CN 116818875 A CN116818875 A CN 116818875A
- Authority
- CN
- China
- Prior art keywords
- vertical graphene
- electrode
- electrochemical
- preset
- sensing electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000002207 metabolite Substances 0.000 claims abstract description 22
- 238000001903 differential pulse voltammetry Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 67
- 229910002804 graphite Inorganic materials 0.000 claims description 40
- 239000010439 graphite Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 40
- 108090000790 Enzymes Proteins 0.000 claims description 37
- 102000004190 Enzymes Human genes 0.000 claims description 37
- 229940088598 enzyme Drugs 0.000 claims description 37
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 37
- 229910052697 platinum Inorganic materials 0.000 claims description 33
- 238000000151 deposition Methods 0.000 claims description 22
- 230000008021 deposition Effects 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 239000004642 Polyimide Substances 0.000 claims description 20
- 239000010408 film Substances 0.000 claims description 20
- 229920001721 polyimide Polymers 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 14
- 238000009713 electroplating Methods 0.000 claims description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims description 8
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 8
- 229910001414 potassium ion Inorganic materials 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- 229940116269 uric acid Drugs 0.000 claims description 8
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229960003638 dopamine Drugs 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 108010092464 Urate Oxidase Proteins 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- -1 graphite alkene Chemical class 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 238000007781 pre-processing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 108010015776 Glucose oxidase Proteins 0.000 claims description 3
- 239000004366 Glucose oxidase Substances 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 3
- 235000012000 cholesterol Nutrition 0.000 claims description 3
- 229940116332 glucose oxidase Drugs 0.000 claims description 3
- 235000019420 glucose oxidase Nutrition 0.000 claims description 3
- 238000005201 scrubbing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 27
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 8
- 239000011540 sensing material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 108010089254 Cholesterol oxidase Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 108010073450 Lactate 2-monooxygenase Proteins 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 108010067973 Valinomycin Proteins 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000010876 biochemical test Methods 0.000 description 1
- ZWYAVGUHWPLBGT-UHFFFAOYSA-N bis(6-methylheptyl) decanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCCCCCC(=O)OCCCCCC(C)C ZWYAVGUHWPLBGT-UHFFFAOYSA-N 0.000 description 1
- 238000009534 blood test Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 239000003710 calcium ionophore Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009535 clinical urine test Methods 0.000 description 1
- FCFNRCROJUBPLU-UHFFFAOYSA-N compound M126 Natural products CC(C)C1NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC1=O FCFNRCROJUBPLU-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- CJAONIOAQZUHPN-KKLWWLSJSA-N ethyl 12-[[2-[(2r,3r)-3-[2-[(12-ethoxy-12-oxododecyl)-methylamino]-2-oxoethoxy]butan-2-yl]oxyacetyl]-methylamino]dodecanoate Chemical compound CCOC(=O)CCCCCCCCCCCN(C)C(=O)CO[C@H](C)[C@@H](C)OCC(=O)N(C)CCCCCCCCCCCC(=O)OCC CJAONIOAQZUHPN-KKLWWLSJSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- AAIMUHANAAXZIF-UHFFFAOYSA-L platinum(2+);sulfite Chemical compound [Pt+2].[O-]S([O-])=O AAIMUHANAAXZIF-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- FCFNRCROJUBPLU-DNDCDFAISA-N valinomycin Chemical compound CC(C)[C@@H]1NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC1=O FCFNRCROJUBPLU-DNDCDFAISA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Abstract
The application relates to the field of sensors, in particular to an electrochemical sensing device based on a vertical graphene microelectrode array and a preparation method thereof. The electrochemical sensing device based on the vertical graphene microelectrode array comprises an electrochemical sensor, wherein the electrochemical sensor consists of the vertical graphene microelectrode array, a counter electrode and a reference electrode; the device also comprises an electrochemical workstation, wherein the electrochemical workstation is used for being connected with the chemical sensor and detecting the concentration of various metabolites in the solution to be detected in real time through a differential pulse voltammetry. The vertical graphene microsensor electrode array can detect various metabolite concentrations of a solution to be detected at the same time, so that the detection efficiency of the sensor is improved, and meanwhile, the detection scene of multiple parameters is adapted; the chemical sensor is connected with the electrochemical workstation, and the concentration of various metabolites in the solution to be detected is detected in real time through a differential pulse voltammetry, so that the generation of impurity current is avoided, and the detection precision of the electrochemical sensor is improved.
Description
Technical Field
The application relates to the field of sensors, in particular to an electrochemical sensing device based on a vertical graphene microelectrode array and a preparation method thereof.
Background
Measurement of metabolite parameters within an organism is typically a biosensor test or an electrochemical sensor test. Biosensing refers to detecting substances or energy in the external environment by using immobilized biosensing materials as recognition elements, and converting the detection result into an electrical signal or other signals convenient to process. Biochemical tests are tests that use chemical reactions within a living organism to detect the state of the organism, such as blood tests, urine tests, etc. As a new branch in the sensor technology field, electrochemical biosensors quantitatively measure physiological parameters in living beings by combining biological and electronic detection technologies. The electrochemical sensor can be used for detecting electrochemical parameters such as redox potential, redox current, redox capacitance and the like of redox reactions, and can also be used for detecting the concentration of electrolyte such as chloride, sulfate radical, hydrogen ions and the like.
In the related art, electrochemical sensing is mainly divided into two major types of enzyme sensing and ion sensing, and various modes such as using a molecularly imprinted polymer exist, and graphene is used as a sensing material to improve the durability and stability of the enzyme sensor, but for miniaturized sensors, due to the limitation of a sensing area, signal current acquired by the graphene sensor is smaller, and good sensing performance cannot be met. The existing sensor mainly measures single parameters and cannot measure a plurality of parameters at the same time; or the integration of the multi-parameter sensor is basically the integration of a single type of sensor, for example, the sensors are all enzyme sensors or all ion sensors, and the detection mode is single. In addition, the solution to be detected is detected by an ampere-time test method, but the method can generate oxidation-reduction current, so that certain interference is caused to electrode detection, and a long-time continuous test can cause burden to a working electrode, so that the electrode sensing precision is reduced. Therefore, the existing electrochemical sensor has a certain limit in the scene application of measuring complex diseases and the like.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
The present application aims to solve at least one of the technical problems existing in the prior art. Therefore, the embodiment of the application provides an electrochemical sensing device based on a vertical graphene microelectrode array and a preparation method thereof, which are beneficial to solving the problems of single sensing function and low sensing detection efficiency of an electrochemical sensor. The electrochemical sensor is composed of the vertical graphene microsensor electrode array, the counter electrode and the reference electrode, the electrochemical workstation is connected with the chemical sensor, the concentration of various metabolites in the solution to be detected is detected in real time through the differential pulse voltammetry, the microsensor electrode array can detect the concentration of various metabolites in the solution to be detected at the same time, the detection efficiency of the sensor is improved, and meanwhile, the detection scene of multiple parameters is adapted; by detecting by using the differential pulse voltammetry, the generation of impurity current is avoided, and the detection precision of the electrochemical sensor is improved.
In a first aspect, an embodiment of the present application provides an electrochemical sensing device based on a vertical graphene microelectrode array, including an electrochemical sensor, where the electrochemical sensor is composed of a vertical graphene microelectrode array, a counter electrode and a reference electrode; and the electrochemical workstation is used for being connected with the chemical sensor and detecting the concentration of various metabolites in the solution to be detected in real time through differential pulse voltammetry.
The technical scheme of the first aspect of the application has at least one of the following advantages or beneficial effects: the electrochemical sensor is composed of the vertical graphene micro-sensing electrode array, the counter electrode and the reference electrode, the micro-sensing electrode array can detect the concentration of various metabolites of the solution to be detected at the same time, the detection efficiency of the sensor is improved, and meanwhile, the detection scene of multiple parameters is adapted; the chemical sensor is connected with the electrochemical workstation, and the concentration of various metabolites in the solution to be detected is detected in real time through a differential pulse voltammetry, so that the generation of impurity current is avoided, and the detection precision of the electrochemical sensor is improved.
Further, the vertical graphene micro-sensing electrode array is used for simultaneously detecting the concentration of various metabolites in the solution to be detected, and comprises one or more of a sodium ion sensing electrode, a calcium ion sensing electrode, a potassium ion sensing electrode, a dopamine sensing electrode, an ascorbic acid sensing electrode and a uric acid sensing electrode.
Further, the vertical graphene microsensor electrode is composed of a laminated structure, and the laminated structure is formed by laminating a vertical graphene layer, a platinum layer and an enzyme layer in sequence on a graphite paper substrate.
Further, the laminated structure further comprises a selective thin film layer, wherein the selective thin film layer is adhered to the platinum layer, and the type of the selective thin film corresponds to the type of the sensing electrode in the vertical graphene micro-sensing electrode array.
Further, the enzyme layer comprises one or more of uricase, lactate, cholesterol, and glucose oxidase.
Further, the diameter of the sensing electrode in the vertical graphene micro-sensing electrode array is 1.7 mm.
In a second aspect, an embodiment of the present application provides a method for preparing an electrochemical sensing device based on a vertical graphene microelectrode array, where the electrochemical sensing device includes an electrochemical sensor, and the method for preparing the electrochemical sensor includes:
the method comprises the steps of taking graphite paper as a base material, and preprocessing the graphite paper by a radio-frequency-assisted plasma enhanced chemical vapor deposition method to obtain deposited vertical graphene;
placing graphite paper with vertical graphene in a magnetron sputtering instrument to sputter a platinum layer to obtain a primary vertical graphene sensing electrode;
uniformly dripping enzyme layers and selective films corresponding to different metabolites on a preset number of primary vertical graphene sensors to obtain a vertical graphene micro-sensing electrode array;
placing polyimide cleaned by ethanol ultrasonic as a substrate material into a preset magnetron sputtering instrument for gold layer deposition pretreatment to obtain a primary counter electrode;
dropping the prepared polyurethane solution on the primary counter electrode, and standing for a first preset time to obtain a counter electrode;
immersing polyimide subjected to magnetron sputtering of a gold layer into silver electroplating solution with preset concentration for electroplating to obtain a primary reference electrode;
carrying out immersion coating on the primary reference electrode by using a methanol solution of polyvinyl butyral, and airing at room temperature to obtain a reference electrode;
and respectively attaching the vertical graphene micro-sensing electrode array, the counter electrode and the reference electrode to a preset polyimide substrate for fixing to obtain the electrochemical sensor.
The technical scheme of the second aspect of the application has at least one of the following advantages or beneficial effects: pretreating graphite paper by adopting a plasma enhanced chemical vapor deposition method to obtain vertical graphene, sequentially sputtering a platinum layer by using the vertical graphene as a substrate in a magnetron manner, and uniformly dripping corresponding catalytic enzyme and a selective film to obtain a vertical graphene sensing electrode, wherein the preparation process is simple and the structure is stable; the vertical graphene micro-sensor has larger specific surface area than the traditional graphene sensing material, and provides good contact sites for enzyme layer-stacked catalytic enzymes, so that the sensitivity and response capability of the vertical graphene micro-sensor electrode are improved. And respectively attaching the vertical graphene micro-sensing electrode array, the counter electrode and the reference electrode to a preset polyimide substrate for fixation to obtain the electrochemical sensor. The prepared electrochemical sensor is matched with a differential pulse voltammetry to detect the concentration of various metabolites in a solution to be detected, so that the vertical graphene material further acquires larger signal intensity on the micro-sensing electrode array, the service life of the enzyme sensor is ensured, and the mechanical performance and detection precision of the electrochemical sensor are improved.
Further, after the polyimide subjected to the magnetron sputtering gold layer is immersed in the silver plating solution provided with the preset concentration for plating, the primary reference electrode is obtained, and the method further comprises:
the primary reference electrode is put into deionized water solution for scrubbing, taken out and naturally dried;
and coating the naturally dried primary reference electrode by using silver chloride ink, and placing the primary reference electrode in an oven to dry at a first preset temperature.
Further, the method for preprocessing the graphite paper by using the graphite paper as a base material through a radio frequency-assisted plasma enhanced chemical vapor deposition method to obtain deposited vertical graphene comprises the following steps:
taking graphite paper as a base material, carrying out deposition treatment on the graphite paper by using first preset radio frequency power, preset total gas mass flow and preset gas pressure,
and in the deposition treatment process, methane gas with preset volume concentration in hydrogen is used as a carbon source, the temperature of the substrate is kept in a preset temperature interval, and the deposition treatment is carried out on the graphite paper for a second preset time to obtain deposited vertical graphene.
Further, the placing the graphite paper with the vertical graphene in a magnetron sputtering instrument to sputter a platinum layer to obtain a primary vertical graphene sensing electrode comprises:
and (3) placing the graphite paper with the vertical graphene in a GVC-2000 magnetron sputtering instrument, assembling a platinum target, and connecting argon and nitrogen for vacuumizing and keeping magnetron sputtering for a third preset time.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application. The objectives and other advantages of the application will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
Fig. 1 is a schematic structural diagram of an electrochemical sensing device based on a vertical graphene microelectrode array according to an embodiment of the present application;
FIG. 2 is a schematic diagram of an electrochemical sensor according to an embodiment of the present application;
FIG. 3 is a schematic view of a laminated structure according to an embodiment of the present application;
fig. 4 is a method for preparing an electrochemical sensor in an electrochemical sensing device based on a vertical graphene microelectrode array according to an embodiment of the present application;
FIG. 5 is a schematic illustration of another method for fabricating an electrochemical sensor in an electrochemical sensing device based on a vertical graphene microelectrode array according to an embodiment of the present application;
FIG. 6 is a flowchart of the steps of S100 in FIG. 4;
fig. 7 is a scanning electron microscope characterization diagram of a surface sensing area of vertical graphene provided by an embodiment of the present application;
fig. 8 is a scanning electron microscope characterization diagram of a sensing area of a vertical graphene through a magnetron sputtering platinum layer, which is provided by the embodiment of the application.
Detailed Description
The present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the description of the present application, plural means two or more. The description of the first and second is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the related art, electrochemical sensing is mainly divided into two major types of enzyme sensing and ion sensing, and various modes such as using a molecularly imprinted polymer exist, and graphene is used as a sensing material to improve the durability and stability of the enzyme sensor, but for miniaturized sensors, due to the limitation of a sensing area, signal current acquired by the graphene sensor is smaller, and good sensing performance cannot be met. Common working electrodes include metal electrodes, mercury electrodes, carbon electrodes, and the like. Because of the interference of active substances in the environmental sample to be detected, the electrochemical sensor has poor long-term use stability, poor target analyte selectivity and low sensitivity, so how to further improve the sensitivity, stability and selectivity of the sensor is an important problem to be solved when the current electrochemical sensor is applied to the field of environmental detection.
The existing sensor mainly measures single parameters and cannot measure a plurality of parameters at the same time; or the integration of the multi-parameter sensor is basically the integration of a single type of sensor, for example, the sensors are all enzyme sensors or all ion sensors, and the detection mode is single. In addition, the solution to be detected is detected by an ampere-time test method, but the method can generate oxidation-reduction current, so that certain interference is caused to electrode detection, and a long-time continuous test can cause burden to a working electrode, so that the electrode sensing precision is reduced. Therefore, the existing electrochemical sensor has a certain limit in the scene application of measuring complex diseases and the like. Therefore, the embodiment of the application provides an electrochemical sensing device based on a vertical graphene microelectrode array and a preparation method thereof, which are beneficial to solving the problems of single sensing function and low sensing detection efficiency of an electrochemical sensor.
Referring to fig. 1, an electrochemical sensing device based on a vertical graphene microelectrode array includes an electrochemical sensor 1000 and an electrochemical workstation (not shown), wherein the electrochemical sensor 1000 is composed of a vertical graphene microelectrode array 100, a counter electrode 200 and a reference electrode 300. The electrochemical workstation is used to connect with the chemical sensor 1000 and detect the concentration of various metabolites in the solution to be measured in real time by differential pulse voltammetry.
The electrochemical sensor is composed of the vertical graphene micro-sensing electrode array, the counter electrode and the reference electrode, the micro-sensing electrode array can detect the concentration of various metabolites of the solution to be detected at the same time, the detection efficiency of the sensor is improved, and meanwhile, the detection scene of multiple parameters is adapted; the chemical sensor is connected with the electrochemical workstation, and the concentration of various metabolites in the solution to be detected is detected in real time through a differential pulse voltammetry, so that the generation of impurity current is avoided, and the detection precision of the electrochemical sensor is improved.
Referring to fig. 2, fig. 2 is a schematic structural diagram of an electrochemical sensor 1000 in another electrochemical sensing device based on a vertical graphene microelectrode array according to an embodiment of the present application, where the electrochemical sensor 1000 is composed of a vertical graphene microelectrode array 100, a counter electrode 200 and a reference electrode 300. The vertical graphene micro-sensing electrode array 100 comprises a sodium ion sensing electrode 10, a calcium ion sensing electrode 20, a potassium ion sensing electrode 30, a dopamine sensing electrode 40, an ascorbic acid sensing electrode 50 and a uric acid sensing electrode 60.
The vertical graphene microsensor electrode array 100 can detect various metabolite concentrations of the solution to be detected at the same time, so that the detection efficiency of the sensor is improved; the vertical graphene microsensor electrode array 100 is connected with a chemical workstation, the concentration of sodium ions, calcium ions, potassium ions, dopamine, ascorbic acid and uric acid in a solution to be detected is detected in real time through a differential pulse voltammetry, the concentration of various metabolites in the solution to be detected is dynamically detected in real time, and the detection scene of multiple parameters is adapted.
The differential pulse voltammetry is used for applying a pulse wave with a linearly-increased excitation voltage to the working electrode, so that the interference of capacitance current generated due to the change of potential along with time to a final test result is eliminated, and the oxidation-reduction current caused by impurities generated due to irregular preparation in the test process can be greatly reduced.
It should be noted that, the vertical graphene micro-sensing electrode array 100 includes one or more of a sodium ion sensing electrode, a calcium ion sensing electrode, a potassium ion sensing electrode, a dopamine sensing electrode, an ascorbic acid sensing electrode, and a uric acid sensing electrode, and may further include one or more of an amino acid sensing electrode, a sugar sensing electrode, a fatty acid sensing electrode, and a vitamin sensing electrode. The embodiment of the application does not limit the type of the sensing electrode of the vertical graphene micro-sensing electrode array 100, and the corresponding sensing electrode can be arranged according to actual requirements.
It should be noted that, in the embodiment of the application, the diameter of the sensing electrode in the vertical graphene micro-sensing electrode array is 1.7 mm, and the specific surface area is larger than that of the traditional graphene sensing material, so that a good contact site is provided for the catalytic enzyme of the enzyme laminated layer 4, and the sensitivity and the response capability of the vertical graphene micro-sensing electrode are improved. The diameter of the sensing electrode in the vertical graphene micro-sensing electrode array can be set according to actual test requirements, and the size of the diameter of the sensing electrode in the vertical graphene micro-sensing electrode array is not limited in the embodiment of the application.
Referring to fig. 3, fig. 3 is a schematic view of a laminated structure, in which a vertical graphene microsensor electrode is composed of a laminated structure composed of a vertical graphene layer 2, a platinum layer 3, and an enzyme layer laminate 4 in this order, with a graphite paper substrate 1. The vertical graphene layer 2 has a larger specific surface area than that of a traditional graphene sensing material, and provides a good contact site for catalyzing enzymes of the enzyme laminated layer 4, so that the sensitivity and the response capability of the vertical graphene microsensor electrode are improved; and secondly, the platinum layer 3 is magnetically sputtered on the vertical graphene layer 2, so that the vertical graphene layer 2 is protected, the stability of a laminated structure is improved, meanwhile, the platinum layer 3 can respond to hydrogen peroxide generated by catalytic enzyme of the enzyme laminated layer 4, and the detection performance of the vertical graphene microsensor electrode is improved.
In the embodiment of the present application, the stacked structure further includes a selective thin film layer (not shown in the figure), where the selective thin film layer is adhered to the platinum layer 3, and the type of the selective thin film corresponds to the type of the sensing electrode in the vertical graphene micro-sensing electrode array 100.
It should be noted that, the selective film layer in the embodiment of the present application includes one or more of a sodium ion selective film layer, a calcium ion selective film layer, a potassium ion selective film layer, a dopamine selective film layer, an ascorbic acid selective film layer, and a uric acid selective film layer, and may further include one or more of an amino acid selective film layer, a saccharide selective film layer, a fatty acid selective film layer, and a vitamin selective film layer. The embodiment of the application does not limit the type of the selective membrane layer, and the corresponding selective membrane layer can be arranged according to actual requirements.
It should be noted that, the enzyme laminated layer 4 includes one or more of uricase, lactate, cholesterol, and glucose oxidase, and the enzyme laminated layer 4 may be set according to actual detection requirements, and the type of the enzyme laminated layer 4 is not limited in the embodiment of the present application.
Referring to fig. 4, fig. 4 is a method for preparing an electrochemical sensing device based on a vertical graphene microelectrode array according to an embodiment of the present application, wherein the electrochemical sensing device includes an electrochemical sensor, the method for preparing an electrochemical sensor includes steps S100 to S800, specifically,
s100: the method comprises the steps of taking graphite paper as a base material, and preprocessing the graphite paper by a radio-frequency-assisted plasma enhanced chemical vapor deposition method to obtain deposited vertical graphene;
s200: placing graphite paper with vertical graphene in a magnetron sputtering instrument to sputter a platinum layer to obtain a primary vertical graphene sensing electrode;
s300: uniformly dripping enzyme layers and selective films which are used for detecting different metabolites on a preset number of primary vertical graphene sensors to obtain a vertical graphene microsensor electrode array;
s400: placing polyimide cleaned by ethanol ultrasonic as a substrate material into a preset magnetron sputtering instrument for gold layer deposition pretreatment to obtain a primary counter electrode;
s500: dripping the prepared polyurethane solution on the primary counter electrode, and standing for a first preset time to obtain a counter electrode;
s600: immersing polyimide subjected to magnetron sputtering of a gold layer into silver electroplating solution with preset concentration for electroplating to obtain a primary reference electrode;
s700: carrying out immersion coating on a primary reference electrode by using a methanol solution of polyvinyl butyral, and airing at room temperature to obtain the reference electrode;
s800: and respectively attaching the vertical graphene micro-sensing electrode array, the counter electrode and the reference electrode to a preset polyimide substrate for fixation to obtain the electrochemical sensor.
In the embodiment of the application, the graphene paper is pretreated by adopting a plasma enhanced chemical vapor deposition method to obtain the vertical graphene, a platinum layer is sequentially and magnetically sputtered by taking the vertical graphene as a substrate, and the corresponding catalytic enzyme and the selective film are uniformly dripped to obtain the vertical graphene sensing electrode, so that the preparation flow is simple and the structure is stable; the vertical graphene micro-sensor has larger specific surface area than the traditional graphene sensing material, and provides good contact sites for enzyme layer-stacked catalytic enzymes, so that the sensitivity and response capability of the vertical graphene micro-sensor electrode are improved. The polyimide cleaned by ethanol ultrasonic is taken as a base material to be placed into a preset magnetron sputtering instrument for pretreatment, and prepared polyurethane solution is dripped and then refined, so that the counter electrode is obtained. And immersing polyimide subjected to magnetron sputtering of the gold layer into silver electroplating solution with preset concentration for electroplating, performing electrochemical deposition silver treatment by a constant pressure method, performing immersion coating by using methanol solution of polyvinyl butyral, and airing at room temperature to obtain the reference electrode. And finally, respectively attaching the vertical graphene micro-sensing electrode array, the counter electrode and the reference electrode to a preset polyimide substrate for fixation to obtain the electrochemical sensor. The prepared electrochemical sensor is matched with a differential pulse voltammetry to detect the concentration of various metabolites in a solution to be detected, so that the vertical graphene material further acquires larger signal intensity on the sensing electrode array, the service life of the enzyme sensor is ensured, and the mechanical performance and detection precision of the electrochemical sensor are improved.
It should be noted that, in the embodiment of the present application, the first preset time is between 6 hours and 8 hours, and the first preset time is set according to the temperature of the preparation environment and the actual requirement, and the embodiment of the present application does not limit the first preset time.
The polyimide cleaned by ethanol ultrasonic is taken as a base material to be placed into a preset magnetron sputtering instrument for pretreatment, the primary counter electrode is obtained by taking the polyimide cleaned by ethanol ultrasonic as the base material, placing the base material into a lattice micro GVC-2000 magnetron sputtering instrument, assembling a gold target, connecting argon and nitrogen, vacuumizing, and performing magnetron sputtering for 10 to 15 minutes to obtain the primary counter electrode.
Referring to fig. 5, fig. 5 is a schematic diagram illustrating another method for manufacturing an electrochemical sensing device based on a vertical graphene microelectrode array according to an embodiment of the present application, including steps S610 to S620, specifically,
s600: immersing polyimide subjected to magnetron sputtering of a gold layer into silver electroplating solution with preset concentration for electroplating to obtain a primary reference electrode;
s610: the primary reference electrode is put into deionized water solution for scrubbing, taken out and naturally dried;
s620: the naturally dried primary reference electrode is coated with silver chloride ink and placed in an oven to be dried at a first preset temperature.
Adding quantitative silver electroplating solution into a beaker, placing polyimide subjected to magnetron sputtering of a gold layer into the electroplating solution for electroplating, performing electrochemical silver deposition in the electroplating solution by using a constant pressure method to obtain a primary reference electrode, placing the primary reference electrode into deionized water solution for gentle rinsing after deposition, taking out and naturally drying; then coated with silver/silver chloride ink and dried in an oven at a first preset temperature. And (3) taking out the sample after drying, immersing and coating the sample by using a methanol solution of polyvinyl butyral, and airing the sample at room temperature to obtain the reference electrode.
The plating by immersing the polyimide subjected to the magnetron sputtering of the gold layer in the silver plating solution provided with the preset concentration includes an electrochemical deposition silver treatment using a constant voltage method, specifically, a deposition treatment using a voltage of 2V for 350 s.
It should be noted that, the first preset temperature is 95 ℃ to 98 ℃, and the first preset temperature can be set according to the actual requirement according to the preparation environment, and the embodiment of the application does not limit the first preset temperature.
Referring to fig. 6, fig. 6 is a flowchart of steps of S100 in fig. 1, including steps S110 to S120, specifically,
s110: taking graphite paper as a base material, carrying out deposition treatment on the graphite paper by using first preset radio frequency power, preset total gas mass flow and preset gas pressure,
s120: and in the deposition treatment process, methane gas with preset volume concentration in hydrogen is used as a carbon source, the temperature of the substrate is kept in a preset temperature interval, and the deposition treatment is carried out on the graphite paper for a second preset time to obtain the deposited vertical graphene.
In the embodiment of the application, graphite paper is used as a base material, the graphite paper is pretreated by a radio frequency-assisted plasma enhanced chemical vapor deposition method, the deposited vertical graphene is obtained specifically by carrying out deposition treatment on the graphite paper by using a first preset radio frequency power, a preset total gas mass flow and a preset gas pressure, methane gas with a preset volume concentration in hydrogen is used as a carbon source in the deposition treatment process, the temperature of a substrate is kept in a preset temperature range, and the deposition treatment is carried out on the graphite paper for a second preset time to obtain the deposited vertical graphene.
The vertical graphene sensing electrode is obtained by taking graphite paper as a base material and carrying out deposition treatment on the graphite paper by a chemical vapor deposition method, and has the advantages of simple preparation flow and stable structure; the vertical graphene micro-sensor has larger specific surface area than the traditional graphene sensing material, and provides good contact sites for enzyme layer-stacked catalytic enzymes, so that the sensitivity and response capability of the vertical graphene micro-sensor electrode are improved.
It should be noted that, in the embodiment of the present application, during the deposition process, the first preset rf power is 1000 to 2000W, the preset total mass flow of gas is 5 to 10sccm, and the gas pressure is maintained at 6 to 12Pa. In the embodiment of the application, the first preset radio frequency power, the preset total gas mass flow and the gas pressure can be set according to the actual requirements in the preparation process, and the embodiment of the application does not limit the magnitudes of the first preset radio frequency power, the preset total gas mass flow and the gas pressure.
In the embodiment of the application, in the deposition process, the preset temperature interval is 600 ℃ to 900 ℃ and the second preset time is 5 to 40 minutes, and the vertical graphene is prepared by adopting methane gas with the volume concentration of 5 to 100% in hydrogen as a carbon source, and simultaneously changing the temperature of the substrate between 600 ℃ and 900 ℃ for 5 to 40 minutes to deposit the vertical graphene.
In one embodiment of the application, placing the graphite paper with the vertical graphene in a magnetron sputtering instrument to sputter a platinum layer to obtain the primary vertical graphene sensing electrode comprises placing the graphite paper with the vertical graphene in a GVC-2000 magnetron sputtering instrument, assembling a platinum target, and connecting argon and nitrogen to perform magnetron sputtering in which vacuum pumping is performed for a third preset time.
And when the vertical graphene stably grows on the graphite paper, placing the prepared vertical graphene in a lattice micro GVC-2000 magnetron sputtering instrument, assembling a platinum target, connecting argon and nitrogen, and then vacuumizing and performing magnetron sputtering to obtain the primary vertical graphene sensing electrode.
It should be noted that, in the embodiment of the present application, the third preset time is 10 to 15 minutes, and the third preset time may be set according to the actual situation in the preparation process, which is not limited in the embodiment of the present application.
In some embodiments of the present application, when preparing the sensing electrode, for the dopamine sensing electrode and the ascorbic acid sensing electrode, the vertical graphene after magnetron sputtering platinum is directly used for corresponding enzyme layer stacking and selective film stacking, so as to obtain the vertical graphene sensing electrode. For uric acid sensing electrodes, the vertical graphene which is subjected to magnetron sputtering of platinum is used as a working electrode to be connected with an electrochemical workstation, a platinum sheet electrode is used as a counter electrode, and silver/silver chloride is used as a reference electrode. Three electrodes were immersed in a platinum sulfite plating solution and electrochemical deposition was performed using a multi-step constant current method, specifically, the first stage was continued to deposit using a forward current of 0.00006A for 10s, the second stage was continued to deposit using a reverse current of 0.00006A for 10s, and the third stage was continued to deposit using a reverse current of 0.004A for 200s. The electrodes were removed after deposition and air dried at room temperature for more than 2 hours. 4wt% bovine serum albumin: 2wt% glutaraldehyde solution: 2wt% uricase solution according to 5:2:1 are mixed in proportion to prepare the uricase selective film, 2 mu l of the film is evenly dripped on the surface of platinum, and the film stands for 6 to 8 hours at room temperature to obtain the uric acid sensing electrode.
In some embodiments of the application, the preparation process of the potassium ion sensing electrode comprises the steps of connecting vertical graphene which completes magnetron sputtering of platinum as a working electrode to an electrochemical workstation, using a platinum sheet electrode as a counter electrode, and using silver/silver chloride as a reference electrode; three electrodes were immersed in a solution using a polymer of monomer ethylene monomer (PEDOT) solution prepared, and electrochemical deposition was performed using a multi-step constant current method, specifically, continuous deposition using a current of 14 μa for 400s. The electrodes were removed after deposition and air dried at room temperature for more than 4 hours. 2% w/w of valinomycin, 0.5% w/w of sodium tetraphenylboron, 32.7% of polyvinyl chloride and 64.7% w/w of diisooctyl sebacate are dissolved in 700 mu L of cyclohexanone in total, 2 mu L of the solution is uniformly dripped on a PEDOT layer, and finally the solution is stood for 6 to 8 hours at room temperature, so that the potassium ion sensing electrode is obtained.
In some embodiments of the application, the preparation process of the calcium ion sensing electrode comprises the steps of connecting vertical graphene which completes magnetron sputtering of platinum as a working electrode to an electrochemical workstation, using a platinum sheet electrode as a counter electrode, and using silver/silver chloride as a reference electrode; mixing 0.46% w/w of calcium ionophore, 0.48% w/w of WNaTPB, 33.02% of PVC and 66.04% w/w of nitrooctyl ether, dissolving 200mg in 1mL of tetrahydrofuran, uniformly dripping 2 μl of the solution onto a PEDOT layer, and finally standing at room temperature for 6-8 hours to obtain the calcium ion sensing electrode.
In some embodiments of the application, the preparation process of the sodium ion sensing electrode comprises connecting vertical graphene with magnetron sputtered platinum as a working electrode to an electrochemical workstation with a platinum sheet electrode as a counter electrode and silver/silver chloride as a reference electrode; to 660ul of tetrahydrofuran, 1% w/w of sodium ion carrier, 65.45% w/w of DOS, 32.7% w/w of PVC and 0.55% w/w of sodium tetraborate were added, and 100mg of the mixture was thoroughly mixed and dissolved, 2. Mu.l of the mixture was uniformly dropped on a PEDOT layer, and finally, the mixture was allowed to stand at room temperature for 6 to 8 hours to obtain a sodium ion sensing electrode.
Referring to fig. 7 and 8, fig. 7 is a scanning electron microscope characterization diagram of a surface sensing region of vertical graphene, and fig. 8 is a scanning electron microscope characterization diagram of a sensing region of vertical graphene through a magnetron sputtered platinum layer. The vertical graphene micro-sensing electrode prepared by adopting the ways of ion-body enhanced chemical vapor deposition, magnetron sputtering and dripping has good electrical performance; after the magnetron sputtering of the platinum layer, a layer of uniform nano platinum black particles can be covered on the premise of ensuring that the original vertical graphene structure is not damaged, so that the conductivity of the material is further improved, and good contact sites are provided for the catalytic enzyme of the enzyme layer stack, so that the sensitivity and the response capability of the vertical graphene microsensor electrode are improved.
While the preferred embodiment of the present application has been described in detail, the present application is not limited to the above embodiment, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present application, and these equivalent modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (10)
1. Electrochemical sensing device based on perpendicular graphite alkene microelectrode array, its characterized in that includes:
the electrochemical sensor consists of a vertical graphene micro-sensing electrode array, a counter electrode and a reference electrode;
and the electrochemical workstation is used for being connected with the chemical sensor and detecting the concentration of various metabolites in the solution to be detected in real time through differential pulse voltammetry.
2. The electrochemical sensing device based on a vertical graphene microelectrode array according to claim 1, wherein the vertical graphene microelectrode array is used for simultaneously detecting the concentration of multiple metabolites in a solution to be detected, and the vertical graphene microelectrode array comprises one or more of a sodium ion sensing electrode, a calcium ion sensing electrode, a potassium ion sensing electrode, a dopamine sensing electrode, an ascorbic acid sensing electrode and a uric acid sensing electrode.
3. The electrochemical sensing device based on a vertical graphene microelectrode array according to claim 2, wherein the vertical graphene microelectrode is composed of a laminated structure, and the laminated structure is composed of a vertical graphene layer, a platinum layer and an enzyme layer laminated in sequence, wherein the laminated structure uses graphite paper as a substrate.
4. The electrochemical sensing device of claim 3, wherein the stacked structure further comprises a selective thin film layer adhered to the platinum layer, the type of selective thin film corresponding to the type of sensing electrode in the vertical graphene micro-sensing electrode array.
5. The electrochemical sensing device based on a vertical graphene microelectrode array according to claim 3, wherein the enzyme layer comprises one or more of uricase, lactate, cholesterol enzyme, and glucose oxidase.
6. The electrochemical sensing device based on a vertical graphene microelectrode array according to claim 2, wherein the diameter of the sensing electrode in the vertical graphene microelectrode array is 1.7 mm.
7. A method for preparing an electrochemical sensing device based on a vertical graphene microelectrode array, the electrochemical sensing device comprising an electrochemical sensor, the method comprising:
the method comprises the steps of taking graphite paper as a base material, and preprocessing the graphite paper by a radio-frequency-assisted plasma enhanced chemical vapor deposition method to obtain deposited vertical graphene;
placing graphite paper with vertical graphene in a magnetron sputtering instrument to sputter a platinum layer to obtain a primary vertical graphene sensing electrode;
uniformly dripping enzyme layers and selective films corresponding to different metabolites on a preset number of primary vertical graphene sensors to obtain a vertical graphene micro-sensing electrode array;
placing polyimide cleaned by ethanol ultrasonic as a substrate material into a preset magnetron sputtering instrument for gold layer deposition pretreatment to obtain a primary counter electrode;
dropping the prepared polyurethane solution on the primary counter electrode, and standing for a first preset time to obtain a counter electrode;
immersing polyimide subjected to magnetron sputtering of a gold layer into silver electroplating solution with preset concentration for electroplating to obtain a primary reference electrode;
carrying out immersion coating on the primary reference electrode by using a methanol solution of polyvinyl butyral, and airing at room temperature to obtain a reference electrode;
and respectively attaching the vertical graphene micro-sensing electrode array, the counter electrode and the reference electrode to a preset polyimide substrate for fixing to obtain the electrochemical sensor.
8. The method for manufacturing an electrochemical sensing device based on a vertical graphene microelectrode array according to claim 7, wherein after the polyimide subjected to the magnetron sputtering of the gold layer is immersed in a silver plating solution provided with a preset concentration for plating, the method further comprises:
the primary reference electrode is put into deionized water solution for scrubbing, taken out and naturally dried;
and coating the naturally dried primary reference electrode by using silver chloride ink, and placing the primary reference electrode in an oven to dry at a first preset temperature.
9. The method for preparing an electrochemical sensing device based on a vertical graphene microelectrode array according to claim 7, wherein the pretreatment of the graphite paper by a radio-frequency-assisted plasma-enhanced chemical vapor deposition method with the graphite paper as a base material to obtain the deposited vertical graphene comprises:
taking graphite paper as a base material, carrying out deposition treatment on the graphite paper by using first preset radio frequency power, preset total gas mass flow and preset gas pressure,
and in the deposition treatment process, methane gas with preset volume concentration in hydrogen is used as a carbon source, the temperature of the substrate is kept in a preset temperature interval, and the deposition treatment is carried out on the graphite paper for a second preset time to obtain deposited vertical graphene.
10. The method for preparing an electrochemical sensing device based on a vertical graphene microelectrode array according to claim 7, wherein the placing the graphite paper with the vertical graphene in a magnetron sputtering instrument for sputtering a platinum layer to obtain a primary vertical graphene sensing electrode comprises:
and (3) placing the graphite paper with the vertical graphene in a GVC-2000 magnetron sputtering instrument, assembling a platinum target, and connecting argon and nitrogen for vacuumizing and keeping magnetron sputtering for a third preset time.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310725515.7A CN116818875A (en) | 2023-06-16 | 2023-06-16 | Electrochemical sensing device based on vertical graphene microelectrode array and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310725515.7A CN116818875A (en) | 2023-06-16 | 2023-06-16 | Electrochemical sensing device based on vertical graphene microelectrode array and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116818875A true CN116818875A (en) | 2023-09-29 |
Family
ID=88119716
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310725515.7A Pending CN116818875A (en) | 2023-06-16 | 2023-06-16 | Electrochemical sensing device based on vertical graphene microelectrode array and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116818875A (en) |
-
2023
- 2023-06-16 CN CN202310725515.7A patent/CN116818875A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN2372689Y (en) | Current biological sensor | |
US6582573B2 (en) | Membrane based electrochemical test device | |
Pundir et al. | Biosensing methods for determination of triglycerides: A review | |
Zuaznabar-Gardona et al. | A wide-range solid state potentiometric pH sensor based on poly-dopamine coated carbon nano-onion electrodes | |
TW548095B (en) | Electrochemical electrode test piece and method for producing the same | |
TWI450967B (en) | Homogeneously-structured nano-catalyst/enzyme composite electrode, fabricating method and application of the same | |
JP3387926B2 (en) | Potentiometric biosensor and method of using the same | |
Ding et al. | Trends in cell-based electrochemical biosensors | |
CN101074963B (en) | Electrode testing strip for inspecting cholesterine by electrochemical method and its production | |
Wu et al. | Amperometric cholesterol biosensor based on zinc oxide films on a silver nanowire–graphene oxide modified electrode | |
CA2700507A1 (en) | Multi-region and potential test sensors, methods, and systems | |
JP2011099849A (en) | Dual-chamber multi-analyte test strip including counter electrode | |
CN105572199A (en) | Working electrode biological reactant and electrode type test strip | |
JP2011095259A (en) | Test meter for use with dual-chamber multi-analyte test strip including counter electrode | |
EP1496354A1 (en) | Substrate determining method | |
Liu et al. | Enzyme biosensors for point-of-care testing | |
US20240085362A1 (en) | Method for improving stability of electrochemical sensor | |
Hassanpour et al. | Direct writing of biocatalytic materials based on pens filled with high-tech enzymatic inks:“Do-it-Yourself” | |
WO1999017115A1 (en) | Membrane based electrochemical test device and related methods | |
CN1900305A (en) | Biological sensor for detecting glutamic pyruvic transaminase | |
Li et al. | An amperometric bienzyme biosensor for rapid measurement of alanine aminotransferase in whole blood | |
CN100396786C (en) | Multiple parameter micro sensor | |
CN115078508B (en) | Electrochemical biosensor and preparation method thereof | |
CN116818875A (en) | Electrochemical sensing device based on vertical graphene microelectrode array and preparation method thereof | |
CN113866235B (en) | Electrochemiluminescence-colorimetric dual-mode sensing detection device based on closed bipolar electrode and construction method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |