CN114878661B - Monoatomic catalyst applied to sensing electrode and preparation method and application thereof - Google Patents
Monoatomic catalyst applied to sensing electrode and preparation method and application thereof Download PDFInfo
- Publication number
- CN114878661B CN114878661B CN202210509752.5A CN202210509752A CN114878661B CN 114878661 B CN114878661 B CN 114878661B CN 202210509752 A CN202210509752 A CN 202210509752A CN 114878661 B CN114878661 B CN 114878661B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- transition metal
- monoatomic
- carbon black
- conductive carbon
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 28
- 239000008103 glucose Substances 0.000 claims abstract description 28
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 150000003624 transition metals Chemical group 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 150000003623 transition metal compounds Chemical class 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 11
- 239000005416 organic matter Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000840 electrochemical analysis Methods 0.000 claims description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 4
- 108010015776 Glucose oxidase Proteins 0.000 claims description 3
- 239000004366 Glucose oxidase Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229940116332 glucose oxidase Drugs 0.000 claims description 3
- 235000019420 glucose oxidase Nutrition 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 108090000790 Enzymes Proteins 0.000 abstract description 21
- 102000004190 Enzymes Human genes 0.000 abstract description 21
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 125000004429 atom Chemical group 0.000 abstract description 6
- 239000006229 carbon black Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 229940088598 enzyme Drugs 0.000 description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 18
- 239000011572 manganese Substances 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000004075 alteration Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 206010012601 diabetes mellitus Diseases 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910017112 Fe—C Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 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
- G01N27/28—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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
- C25B11/079—Manganese dioxide; Lead dioxide
-
- 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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
- G01N27/3272—Test elements therefor, i.e. disposable laminated substrates with electrodes, reagent and channels
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Hematology (AREA)
- Biophysics (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a single-atom catalyst applied to a sensing electrode, which consists of a carbon carrier and transition metal atoms, wherein the carbon carrier is formed by conducting carbon black and nitrogenous organic matters through high-temperature heat treatment; the transition metal atoms interact with the N atoms in the carbon support and are anchored to the carbon support surface in the form of monoatoms. The transition metal elements in the single-atom catalyst provided by the invention are uniformly distributed on the surface of the carbon carrier in the form of atoms; in the detection of glucose, the monoatomic catalyst shows sensitivity and detection limit obviously superior to those of the original conductive carbon black by virtue of high reactivity of monoatomic metal center. The improvement of the performance of the carbon-based material can reduce the dosage of biological enzyme in practical application and reduce the production cost.
Description
Technical Field
The invention belongs to the technical field of biological sensing, and particularly relates to a single-atom catalyst applied to a sensing electrode, a preparation method and application thereof.
Background
Diabetes is a serious chronic disease threatening the health and life of modern people, and monitoring the blood sugar concentration in human bodies is a basic measure for nursing diabetes patients, so that the development of an efficient and convenient blood sugar sensing technology has important significance for the diagnosis and treatment of diabetes. Colorimetry, high-efficiency chromatography, photoinduced luminescence and the like are all common methods for researching and detecting glucose, however, most of the methods are complex in operation, high in cost and long in time, and are difficult to further widely apply. In recent years, electrochemical methods have become a research hotspot in the field of biosensing due to the characteristics of high sensitivity, low cost, easy miniaturization and the like.
The first generation of enzymatic electrochemical sensors is currently the dominant technology for blood glucose detection, which is well developed, however the sensitivity and accuracy are still limited. Meanwhile, the enzyme molecule has complex fixing steps and is easy to be inactivated due to the influence of environmental factors, and the performance improvement and the cost control of the sensor are also hindered.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a single-atom catalyst applied to a sensing electrode, a preparation method and application thereof.
The invention provides a single-atom catalyst applied to a sensing electrode, which consists of a carbon carrier and transition metal atoms, wherein the carbon carrier is formed by conducting carbon black and nitrogenous organic matters through high-temperature heat treatment; the transition metal atoms interact with the N atoms in the carbon support and are anchored to the carbon support surface in the form of monoatoms.
Preferably, the conductive carbon black is selected from one of KJ600, BP2000, XC72 and N326;
The nitrogen-containing organic matter is selected from one of 2,2' -bipyridine, melamine, phenanthroline and urea;
The transition metal element is selected from one of Fe, co, cu and Mn.
Preferably, the mass ratio of the conductive carbon black to the nitrogen-containing organic matter is 1 (1-5);
the mass ratio of the transition metal atoms to the conductive carbon black is (1-2): 100.
The invention also provides a preparation method of the monoatomic catalyst, which comprises the following steps:
a) Mixing conductive carbon black, a transition metal compound and a solvent, and drying to obtain solid powder;
B) And mixing the solid powder with a nitrogen-containing organic matter and calcining to obtain the monoatomic catalyst.
Preferably, the transition metal compound is selected from one of ferric trichloride hexahydrate, cobalt nitrate hexahydrate, cupric chloride dihydrate and manganese chloride tetrahydrate.
Preferably, the solvent is water or ethanol.
Preferably, the calcination is carried out in an inert atmosphere at a temperature of 800-900 ℃ for a time of 1-2 hours.
The invention also provides application of the single-atom catalyst in glucose detection.
The invention also provides an electrochemical test paper for detecting glucose, which comprises the monoatomic catalyst.
The invention also provides a flexible electrode for detecting glucose, which comprises the monoatomic catalyst.
Compared with the prior art, the invention provides a single-atom catalyst applied to a sensing electrode, wherein the single-atom catalyst consists of a carbon carrier and transition metal atoms, and the carbon carrier is formed by conducting carbon black and nitrogenous organic matters through high-temperature heat treatment; the transition metal atoms interact with the N atoms in the carbon support and are anchored to the carbon support surface in the form of monoatoms. The transition metal elements in the single-atom catalyst provided by the invention are uniformly distributed on the surface of the carbon carrier in the form of atoms; in the detection of glucose, the monoatomic catalyst shows sensitivity and detection limit obviously superior to those of the original conductive carbon black by virtue of high reactivity of monoatomic metal center. The improvement of the performance of the carbon-based material can reduce the dosage of biological enzyme in practical application and reduce the production cost.
Drawings
FIG. 1 is a transmission and scanning electron microscope image of Fe monoatoms, co monoatoms, cu monoatoms, and Mn monoatomic catalysts prepared in examples 1 to 4 of the present invention;
FIG. 2 is a spherical aberration correcting high angle annular dark field scanning transmission electron microscope image of Fe monoatoms, co monoatoms, cu monoatoms, and Mn monoatomic catalysts prepared in examples 1 to 4 of the present invention;
FIG. 3 is a schematic diagram and a schematic diagram of a device for macro-scale preparation of the monoatomic catalyst prepared in examples 1 to 4 according to the present invention;
FIG. 4 is a graph comparing the performance of the monoatomic catalysts prepared according to examples 1-4 of the present invention with the performance of the original conductive carbon black to detect hydrogen peroxide;
FIG. 5 is a graph comparing the performance of the monoatomic catalysts prepared according to examples 1 to 4 of the present invention with that of the original conductive carbon black for detecting glucose;
FIG. 6 is a graph comparing the performance of the Fe monoatomic catalyst prepared according to example 1 of the present invention with that of the original conductive carbon black for detecting glucose at different enzyme amounts.
Detailed Description
The invention provides a single-atom catalyst applied to a sensing electrode, which consists of a carbon carrier and transition metal atoms, wherein the carbon carrier is formed by conducting carbon black and nitrogenous organic matters through high-temperature heat treatment; the transition metal atoms interact with the N atoms in the carbon support and are anchored to the carbon support surface in the form of monoatoms.
Wherein the conductive carbon black is selected from one of KJ600, BP2000, XC72 and N326.
The nitrogen-containing organic matter is selected from one of 2,2' -bipyridine, melamine, phenanthroline and urea;
The transition metal element is selected from one of Fe, co, cu and Mn.
The mass ratio of the conductive carbon black to the nitrogen-containing organic matter is 1 (1-5), preferably 1:1, 1:2, 1:3, 1:4, 1:5, or any value between 1 (1-5);
The mass ratio of the transition metal atoms to the conductive carbon black is (1-2): 100, preferably 1:100, 1.2:100, 1.4:100, 1.6:100, 1.8:100, 2.0:100, or any value between (1-2): 100.
In the invention, N species generated by pyrolysis of the nitrogen-containing organic matters can be combined with metal atoms to form an M-Nx structure at a higher temperature, so that the metal atoms are effectively anchored and prevented from being aggregated; the transition metal element is uniformly distributed on the surface of the carbon carrier in the form of atoms.
The invention also provides a preparation method of the single-atom catalyst, which comprises the following steps:
a) Mixing conductive carbon black, a transition metal compound and a solvent, and drying to obtain solid powder;
B) And mixing the solid powder with a nitrogen-containing organic matter and calcining to obtain the monoatomic catalyst.
Firstly, mixing conductive carbon black, a transition metal compound and a solvent to obtain a mixed dispersion liquid.
Specifically, the manner of mixing is not particularly limited in the present invention, and the conductive carbon black and the transition metal compound may be dispersed in a solvent, respectively.
That is, a conductive carbon black is dispersed in a solvent to obtain a dispersion of the conductive carbon black;
Dispersing the transition metal compound in a solvent to obtain a transition metal compound solution. Wherein the concentration of the transition metal compound in the transition metal compound solution is 0.3 to 1.0mg/mL, preferably 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or any value between 0.3 and 1.0 mg/mL. Wherein the transition metal compound is selected from one of ferric trichloride hexahydrate, cobalt nitrate hexahydrate, cupric chloride dihydrate and manganese chloride tetrahydrate.
Then, the dispersion of the conductive carbon black is mixed with the transition metal compound solution, and the dispersion is mixed.
Subsequently, the mixed dispersion is dried. The drying is a drying means well known to those skilled in the art, and there is no particular limitation to the present application, and in a specific example, the drying is performed by spin-evaporation at 50 to 60 ℃.
The solid powder is mixed with a nitrogen-containing organic matter and calcined, so that N species generated by pyrolysis of the nitrogen-containing organic matter can be combined with metal atoms to form an M-Nx structure, and metal elements are effectively anchored on the surface of the carbon carrier in a single-atom form.
The calcination is carried out in an inert atmosphere at a temperature of 800-900 ℃, preferably 800, 820, 840, 860, 880, 900, or any value between 800-900 ℃ for a time of 1-2 hours, preferably 1, 1.5, 2, or 1-2 hours; in a specific embodiment, the inert atmosphere is argon.
The application also provides application of the single-atom catalyst, in particular to application of the single-atom catalyst as a catalyst in the aspect of glucose content detection.
The application of the single-atom catalyst means that the single-atom catalyst can catalyze hydrogen peroxide to generate oxidation reaction under a certain potential after an electrode is modified, the hydrogen peroxide is generated by reduction of oxygen under the action of enzyme molecules, and the generated current signal and the concentration of glucose show a certain linear relation. The application can be further used for manufacturing electrochemical test paper, flexible electrodes and the like. In particular embodiments of the present application, the single-atom catalyst exhibits sensitivity and detection limits that are significantly better than the original conductive carbon black.
The invention also provides an electrochemical test paper for detecting glucose, which comprises the monoatomic catalyst.
The invention also provides a flexible electrode for detecting glucose, which comprises the monoatomic catalyst.
The preparation method of the single-atom catalyst provided by the invention is simple and feasible, and can be used for mass production, and referring to fig. 3, fig. 3 is a device diagram and a physical diagram of macro-preparation of the single-atom catalyst prepared according to embodiments 1-4 of the invention. In fig. 3, a is a mixing process of conductive carbon black, a transition metal compound and a solvent, b is a rotary evaporator, c is a ball mill, d is a large-diameter tube furnace, and e is a catalyst powder obtained by macro preparation. The single-atom catalyst provided by the invention has great application potential in biological sensing and has high-efficiency detection function on glucose. The invention is suitable for the production of electrochemical test paper, flexible electrode and other products, can greatly reduce the use amount of biological enzyme in actual detection, and effectively reduces the cost.
In order to further understand the present invention, the monoatomic catalyst applied to the sensing electrode, the preparation method and the application thereof provided by the present invention are described below with reference to examples, and the scope of the present invention is not limited by the following examples.
Example 1:
preparation of Fe monoatomic catalyst:
(1) Dispersing 100mg of conductive carbon black in 90mL of water, and performing ultrasonic treatment for 30min; preparing 10mL of 0.5mg/mL ferric trichloride hexahydrate aqueous solution; then mixing the two solutions, and stirring for more than 6 hours;
(2) Spin-evaporating the obtained mixed solution at 50-60deg.C to completely volatilize solvent to obtain Fe-C solid powder;
(3) Mixing the obtained Fe-C solid powder with 500mg melamine, and grinding for 1h;
(4) Placing the obtained solid powder into a porcelain boat, then placing the porcelain boat into a tube furnace, sealing and introducing inert gas, heating to 900 ℃ under inert atmosphere, calcining for 1h, naturally cooling to room temperature, and taking out to obtain the Fe monoatomic catalyst, wherein the morphology of the material is shown in the figure 1; as shown in fig. 2, it was observed under a spherical aberration correcting transmission electron microscope that Fe monoatoms were uniformly distributed on the nitrogen-doped carbon support.
FIG. 1 shows transmission and scanning electron microscope images of Fe monoatoms, co monoatoms, cu monoatoms, and Mn monoatomic catalysts prepared in examples 1 to 4 of the present invention. In fig. 1, a corresponds to an Fe monoatomic catalyst, b corresponds to a Co monoatomic catalyst, c corresponds to a Cu monoatomic catalyst, and d corresponds to an Mn monoatomic catalyst.
FIG. 2 is a spherical aberration correcting high angle annular dark field scanning transmission electron microscope image of Fe monoatoms, co monoatoms, cu monoatoms, and Mn monoatomic catalysts prepared in examples 1 to 4 of the present invention. In fig. 2, a corresponds to an Fe monoatomic catalyst, b corresponds to a Co monoatomic catalyst, c corresponds to a Cu monoatomic catalyst, and d corresponds to an Mn monoatomic catalyst.
Example 2
Preparation of Co monoatomic catalyst:
(1) Dispersing 100mg of conductive carbon black in 90mL of water, and performing ultrasonic treatment for 30min; preparing 10mL of 1.0mg/mL cobalt nitrate hexahydrate aqueous solution; then mixing the two solutions, and stirring for more than 6 hours;
(2) Spin-evaporating the obtained mixed solution at 50-60deg.C to completely volatilize solvent to obtain Co-C solid powder;
(3) Mixing the obtained Co-C solid powder with 100mg of 2,2' -bipyridine, and grinding for 1h;
(4) Placing the obtained solid powder into a porcelain boat, then placing the porcelain boat into a tube furnace, sealing and introducing inert gas, heating to 800 ℃ under inert atmosphere, calcining for 2 hours, naturally cooling to room temperature, and taking out to obtain a Co single-atom catalyst, wherein the morphology of the material is shown in the figure 1; as shown in FIG. 2, co monoatoms were observed to be uniformly distributed on the nitrogen-doped carbon support under an spherical aberration correcting transmission electron microscope.
Example 3
Preparation of Cu monoatomic catalyst:
(1) Dispersing 100mg of conductive carbon black in 90mL of water, and performing ultrasonic treatment for 30min; preparing 10mL of copper chloride dihydrate aqueous solution with the concentration of 0.3 mg/mL; then mixing the two solutions, and stirring for more than 6 hours;
(2) Spin-evaporating the obtained mixed solution at 50-60deg.C to completely volatilize solvent to obtain Cu-C solid powder;
(3) Mixing the obtained Cu-C solid powder with 500mg of melamine, and grinding for 1h;
(4) Placing the obtained solid powder into a porcelain boat, then placing the porcelain boat into a tube furnace, sealing and introducing inert gas, heating to 900 ℃ under inert atmosphere, calcining for 1h, naturally cooling to room temperature, and taking out to obtain a Cu monoatomic catalyst, wherein the morphology of the material is shown in the figure 1; as shown in fig. 2, it was observed under an spherical aberration correcting transmission electron microscope that Cu monoatoms were uniformly distributed on the nitrogen-doped carbon support.
Example 4
Preparation of Mn monoatomic catalyst:
(1) Dispersing 100mg of conductive carbon black in 90mL of water, and performing ultrasonic treatment for 30min; preparing 10mL of 0.5mg/mL manganese chloride tetrahydrate aqueous solution; then mixing the two solutions, and stirring for more than 6 hours;
(2) Spin-evaporating the obtained mixed solution at 50-60deg.C to completely volatilize solvent to obtain Mn-C solid powder;
(3) Mixing the obtained Mn-C solid powder with 500mg of melamine, and grinding for 1h;
(4) Placing the obtained solid powder into a porcelain boat, then placing the porcelain boat into a tube furnace, sealing and introducing inert gas, heating to 900 ℃ under inert atmosphere, calcining for 1h, naturally cooling to room temperature, and taking out to obtain the Mn monoatomic catalyst, wherein the morphology of the material is shown in the figure 1; as shown in FIG. 2, mn monoatoms were observed to be uniformly distributed on the nitrogen-doped carbon support under an spherical aberration correcting transmission electron microscope.
Example 5
Glucose sensing Performance test was performed on Fe, co, cu, mn monoatomic catalysts prepared in examples 1 to 4:
(1) The hydrogen peroxide sensing performance was evaluated by dropping 10 μl of catalyst dispersion (a) consisting of 2mg/mL of monoatomic catalyst, ethanol/water (v/v=1:1) and 10 μl/mL of Nafion onto a clean glassy carbon electrode as a working electrode. The test was performed using a three electrode system, the reference electrode was an Ag/AgCl electrode, the counter electrode was Pt wire, and the electrolyte was a1 XPBS buffer solution. The hydrogen peroxide sensing performance of the single-atom catalysts prepared in examples 1-4 compared with that of the original conductive carbon black is shown in FIG. 4; fig. 4 is a graph comparing the performance of the monoatomic catalysts prepared according to examples 1 to 4 of the present invention with that of the original conductive carbon black to detect hydrogen peroxide. In FIG. 4, fe 1 -CN represents a Fe monoatomic catalyst, cu 1 -CN represents a Cu monoatomic catalyst, co 1 -CN represents a Co monoatomic catalyst, mn 1 -CN represents a Mn monoatomic catalyst, C represents an original conductive carbon black, a graph a in FIG. 4 shows a continuous ampere-time response curve of each catalyst-modified electrode to hydrogen peroxide, and b graph b shows a relation curve between current response and hydrogen peroxide concentration obtained from the results of the graph a. It can be seen that the single-atom catalyst has higher sensitivity, wherein the detection effect of the Fe single-atom catalyst is optimal, because the high activity of the single-atom metal center further promotes the oxidation reaction of hydrogen peroxide.
(2) The glucose sensing performance was evaluated by dropping 15. Mu.L of a catalyst dispersion (B) consisting of 2mg/mL of a monoatomic catalyst (500. Mu.L), glucose oxidase (1 mL) and Nafion (50. Mu.L) onto a clean glass carbon electrode as a working electrode, and the amount of enzyme on the electrode was 0.02 to 0.2U. The test was performed using a three electrode system, the reference electrode was an Ag/AgCl electrode, the counter electrode was Pt wire, and the electrolyte was a1 XPBS buffer solution. Comparison of glucose sensing performance of the monatomic catalysts prepared in examples 1 to 4 with the original conductive carbon black referring to fig. 5, fig. 5 is a graph showing comparison of the performance of the monatomic catalysts prepared in examples 1 to 4 according to the present invention with the original conductive carbon black for detecting glucose, i.e., a graph showing the relationship between the current response of each catalyst-modified electrode to glucose and the glucose concentration. In FIG. 5, fe 1 -CN-0.2U represents that the Fe monoatomic catalyst and 0.2U of enzyme are dripped on the working electrode, cu 1 -CN-0.2U represents that the Cu monoatomic catalyst and 0.2U of enzyme are dripped on the working electrode, co 1 -CN-0.2U represents that the Co monoatomic catalyst and 0.2U of enzyme are dripped on the working electrode, mn 1 -CN-0.2U represents that the working electrode is dripped with Mn monoatomic catalyst and 0.2U enzyme, C-0.2U represents that the working electrode is dripped with original conductive carbon black and 0.2U enzyme. It can be seen from fig. 5 that the monoatomic catalyst has superior sensitivity. FIG. 6 is a graph comparing the performance of the Fe monoatomic catalyst prepared according to example 1 of the present invention with that of the original conductive carbon black for detecting glucose at different enzyme amounts. In FIG. 6, fe 1 -CN-0.2U represents that the Fe monoatomic catalyst and 0.2U of enzyme are dripped on the working electrode, fe 1 -CN-0.04U represents that the Fe monoatomic catalyst and 0.04U of enzyme are dripped on the working electrode, fe 1 -CN-0.02U represents that the Fe monoatomic catalyst and 0.02U of enzyme are dripped on the working electrode, C-0.2U represents that the original conductive carbon black and 0.2U enzyme are dripped on the working electrode, wherein a graph a in FIG. 6 shows continuous ampere-time response curves of the Fe monoatomic catalyst and the original conductive carbon black to glucose under different enzyme amounts, b graph b shows detection limits of the Fe monoatomic catalyst and the original conductive carbon black for measuring glucose under the enzyme amount of 0.2U, and C graph C shows a relation curve between current response and glucose concentration obtained according to the result of the graph a. As can be seen from fig. 6, the Fe monoatomic catalyst not only has a lower detection limit, but also has detection sensitivity comparable to that of carbon black when the enzyme content in the Fe monoatomic catalyst is reduced to 10% of that in the carbon black, and the result shows that the introduction of the monoatomic catalyst can greatly reduce the use of the enzyme in glucose sensing, thereby being beneficial to controlling the cost and improving the stability.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The application of the single-atom catalyst in glucose detection is characterized in that the single-atom catalyst consists of a carbon carrier and transition metal atoms, wherein the carbon carrier is formed by calcining conductive carbon black and nitrogen-containing organic matters at 800-900 ℃ for 1-2 hours; the nitrogen-containing organic matter is selected from one of 2,2' -bipyridine, melamine, phenanthroline and urea; the transition metal atoms interact with nitrogen atoms in the carbon support and are anchored to the carbon support surface in the form of monoatoms; the transition metal is Fe;
And (3) dropwise coating a monoatomic catalyst and glucose oxidase on the working electrode, wherein the content of the glucose oxidase is 0.02U-0.2U.
2. The use according to claim 1, wherein the conductive carbon black is selected from one of KJ600, BP2000, XC72 and N326.
3. The use according to claim 1, wherein the mass ratio of the conductive carbon black to the nitrogen-containing organic matter is 1 (1-5);
the mass ratio of the transition metal atoms to the conductive carbon black is (1-2) 100.
4. The use according to claim 1, characterized in that the preparation method of the monoatomic catalyst comprises the following steps:
a) Mixing conductive carbon black, a transition metal compound and a solvent, and drying to obtain solid powder;
B) And mixing the solid powder with a nitrogen-containing organic matter and calcining to obtain the monoatomic catalyst.
5. The use according to claim 4, wherein the transition metal compound is ferric trichloride hexahydrate.
6. The use according to claim 4, wherein the solvent is water or ethanol.
7. The use according to claim 4, wherein the calcination is carried out under an inert atmosphere.
8. An electrochemical test strip for detecting glucose, comprising a monoatomic catalyst for use according to any one of claims 1 to 7.
9. A flexible electrode for detecting glucose comprising a monoatomic catalyst for use according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210509752.5A CN114878661B (en) | 2022-05-11 | 2022-05-11 | Monoatomic catalyst applied to sensing electrode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210509752.5A CN114878661B (en) | 2022-05-11 | 2022-05-11 | Monoatomic catalyst applied to sensing electrode and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114878661A CN114878661A (en) | 2022-08-09 |
| CN114878661B true CN114878661B (en) | 2024-08-16 |
Family
ID=82674819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210509752.5A Active CN114878661B (en) | 2022-05-11 | 2022-05-11 | Monoatomic catalyst applied to sensing electrode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114878661B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739182B (en) * | 2022-11-17 | 2024-01-16 | 合肥机数量子科技有限公司 | Peroxide mimic enzyme containing monodisperse iron atoms, and preparation method and application thereof |
| CN115739161B (en) * | 2022-12-13 | 2024-07-02 | 南京理工大学 | Iron single-atom catalyst, preparation method thereof and application thereof in catalytic reaction for preparing tetrazole anion salt |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108982631A (en) * | 2018-07-26 | 2018-12-11 | 中国科学院山西煤炭化学研究所 | A kind of monatomic metal/composite material of graphene and its preparation method and application |
| CN109908904A (en) * | 2019-04-11 | 2019-06-21 | 中国科学院理化技术研究所 | A kind of monatomic catalyst of transition metal and its preparation method and application |
| CN113786853A (en) * | 2021-08-06 | 2021-12-14 | 中国科学院化学研究所 | Monoatomic catalyst and preparation method thereof, microelectrode and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105529475B (en) * | 2015-12-30 | 2018-02-13 | 中国科学院长春应用化学研究所 | A kind of catalyst of platinum single atomic dispersion and preparation method thereof |
| CN108242549B (en) * | 2016-12-27 | 2021-08-17 | 中国科学技术大学 | Catalyst with dispersed VIII group single atoms and preparation method thereof |
| CN106876728B (en) * | 2017-02-14 | 2020-01-03 | 中国科学技术大学 | High-density transition metal monoatomic load graphene-based catalyst and preparation method thereof |
| CN107799779B (en) * | 2017-10-23 | 2021-01-12 | 清华大学 | Iridium monatomic catalyst for direct formic acid fuel cell and preparation method thereof |
| CN110449177B (en) * | 2019-08-19 | 2021-01-15 | 联科华技术有限公司 | Multifunctional monatomic catalyst for air comprehensive purification and preparation method thereof |
| CN111384409B (en) * | 2020-02-25 | 2021-05-11 | 南京师范大学 | Nitrogen-doped graphite alkyne-riveted transition metal monoatomic catalyst and preparation method and application thereof |
| CN113430566A (en) * | 2021-06-24 | 2021-09-24 | 中国科学技术大学 | Iron monatomic catalyst, preparation method thereof and application thereof in electrolytic water oxygen evolution reaction |
-
2022
- 2022-05-11 CN CN202210509752.5A patent/CN114878661B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108982631A (en) * | 2018-07-26 | 2018-12-11 | 中国科学院山西煤炭化学研究所 | A kind of monatomic metal/composite material of graphene and its preparation method and application |
| CN109908904A (en) * | 2019-04-11 | 2019-06-21 | 中国科学院理化技术研究所 | A kind of monatomic catalyst of transition metal and its preparation method and application |
| CN113786853A (en) * | 2021-08-06 | 2021-12-14 | 中国科学院化学研究所 | Monoatomic catalyst and preparation method thereof, microelectrode and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114878661A (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Cobalt phosphide nanowire array as an effective electrocatalyst for non-enzymatic glucose sensing | |
| Zhang et al. | CuO nanowires based sensitive and selective non-enzymatic glucose detection | |
| Yang et al. | Enzyme-free sensing of hydrogen peroxide and glucose at a CuS nanoflowers modified glassy carbon electrode | |
| Salimi et al. | Non-enzymatic glucose detection free of ascorbic acid interference using nickel powder and nafion sol–gel dispersed renewable carbon ceramic electrode | |
| Tyagi et al. | NiO nanoparticle-based urea biosensor | |
| CN114878661B (en) | Monoatomic catalyst applied to sensing electrode and preparation method and application thereof | |
| Zheng et al. | Carbon nanohorns enhanced electrochemical properties of Cu-based metal organic framework for ultrasensitive serum glucose sensing | |
| Salimi et al. | Electrochemical properties and electrocatalytic activity of FAD immobilized onto cobalt oxide nanoparticles: application to nitrite detection | |
| Zhang et al. | A novel nonenzymatic sensor based on LaNi0. 6Co0. 4O3 modified electrode for hydrogen peroxide and glucose | |
| Lu et al. | Nonenzymatic hydrogen peroxide electrochemical sensor based on carbon-coated SnO2 supported Pt nanoparticles | |
| Liu et al. | Preparation of electrochemical sensor based on the novel NiO quantum dots modified Cu/Cu2O 3D hybrid electrode and its application for non-enzymatic detection of glucose in serums and beverages | |
| Balla et al. | Co3O4 nanoparticles supported mesoporous carbon framework interface for glucose biosensing | |
| Jiang et al. | Glucose electrooxidation in alkaline medium: Performance enhancement of PdAu/C synthesized by NH3 modified pulse microwave assisted polyol method | |
| Dönmez et al. | Preparation of carbon paste electrodes including poly (styrene) attached glycine–Pt (IV) for amperometric detection of glucose | |
| Dönmez | Green synthesis of zinc oxide nanoparticles using Zingiber officinale root extract and their applications in glucose biosensor | |
| Salarizadeh et al. | NiO–MoO3 nanocomposite: A sensitive non-enzymatic sensor for glucose and urea monitoring | |
| Yi et al. | A highly sensitive nonenzymatic glucose sensor based on nickel oxide–carbon nanotube hybrid nanobelts | |
| Li et al. | Coaxial electrospinning synthesis of size-tunable CuO/NiO hollow heterostructured nanofibers: Towards detection of glucose level in human serum | |
| Dhara et al. | Cupric oxide modified screen printed electrode for the nonenzymatic glucose sensing | |
| Ge et al. | Self-template formation of porous Co 3 O 4 hollow nanoprisms for non-enzymatic glucose sensing in human serum | |
| CN107132259B (en) | Doped graphene-based cholesterol sensor and preparation and application thereof | |
| Qian et al. | Recent advances in electrochemical sensors based on palladium nanoparticles | |
| CN109682877B (en) | Electrochemical sensor for detecting glucose | |
| Luo et al. | A ultrasensitive nonenzymatic glucose sensor based on Cu2O polyhedrons modified Cu electrode | |
| CN113777144A (en) | Electrochemical sensor for detecting dopamine in gastric juice and preparation 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |