CN114878661A - Monatomic catalyst applied to sensing electrode and preparation method and application thereof - Google Patents
Monatomic catalyst applied to sensing electrode and preparation method and application thereof Download PDFInfo
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- CN114878661A CN114878661A CN202210509752.5A CN202210509752A CN114878661A CN 114878661 A CN114878661 A CN 114878661A CN 202210509752 A CN202210509752 A CN 202210509752A CN 114878661 A CN114878661 A CN 114878661A
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- 238000002360 preparation method Methods 0.000 title claims description 15
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- 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
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 239000008103 glucose Substances 0.000 claims abstract description 28
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- 239000000843 powder Substances 0.000 claims description 20
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- 238000000034 method Methods 0.000 claims description 8
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- 238000001035 drying Methods 0.000 claims description 6
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- 238000000840 electrochemical analysis Methods 0.000 claims description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 4
- 229910052742 iron Inorganic materials 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
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 4
- 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
- 238000012360 testing method Methods 0.000 claims description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
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- 230000005540 biological transmission Effects 0.000 description 8
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
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- 239000002184 metal Substances 0.000 description 3
- 238000002390 rotary evaporation 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
- 241000282414 Homo sapiens Species 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 208000017667 Chronic Disease Diseases 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
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- 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
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- G01—MEASURING; TESTING
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- 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
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Abstract
The invention provides a monatomic 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 nitrogen-containing organic matters after high-temperature heat treatment; the transition metal atom interacts with the N atom in the carbon support and is anchored to the carbon support surface in the form of a single atom. Transition metal elements in the monatomic catalyst provided by the invention are uniformly distributed on the surface of a carbon carrier in an atomic form; in the detection of glucose, the monatomic catalyst shows sensitivity and detection limit obviously superior to those of the original conductive carbon black by virtue of the high reactivity of the monatomic metal center. The improvement of the performance of the carbon-based material can reduce the dosage of the biological enzyme in practical application and reduce the production cost.
Description
Technical Field
The invention belongs to the technical field of biosensing, and particularly relates to a monatomic catalyst applied to a sensing electrode, and a preparation method and application thereof.
Background
Diabetes is a major chronic disease threatening the health and life of modern human beings, and monitoring blood sugar concentration in a human body is a basic measure for nursing diabetic patients, so that the development of an efficient and convenient blood sugar sensing technology has important significance for the diagnosis and treatment of diabetes. Colorimetric methods, high performance chromatography, light-induced emission methods, and the like are common methods for detecting glucose, however, most of these methods are complicated to operate, high in cost, long in time, and difficult to be widely applied. In recent years, electrochemical methods have become a research hotspot in the field of biosensing due to the characteristics of high sensitivity, low cost, easiness in miniaturization and the like.
The first generation enzymatic electrochemical sensor is the mainstream technology for blood sugar detection at present, and the technology is developed to be mature, but the sensitivity and the accuracy are still limited. Meanwhile, the enzyme molecules are complicated in fixing step and are easily inactivated by 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 this, the technical problem to be solved by the present invention is to provide a monatomic catalyst applied to a sensing electrode, and a preparation method and an application thereof, and the catalyst provided by the present invention can greatly improve the detection sensitivity of glucose, reduce the dosage of enzyme, and improve the detection stability.
The invention provides a monatomic 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 nitrogen-containing organic matters after high-temperature heat treatment; the transition metal atom interacts with the N atom in the carbon support and is anchored to the carbon support surface in the form of a single atom.
Preferably, the conductive carbon black is one selected from KJ600, BP2000, XC72, and N326;
the nitrogen-containing organic matter is selected from one of 2,2' -bipyridyl, 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 monatomic 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 monatomic catalyst.
Preferably, the transition metal compound is one selected from the group consisting of ferric chloride 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 the temperature of 800-900 ℃ for 1-2 h.
The invention also provides an application of the monatomic catalyst in glucose detection.
The invention also provides an electrochemical test paper for detecting glucose, which comprises the monatomic catalyst.
The invention also provides a flexible electrode for detecting glucose, which comprises the monatomic catalyst.
Compared with the prior art, the invention provides the monatomic catalyst applied to the sensing electrode, the monatomic catalyst consists of a carbon carrier and transition metal atoms, and the carbon carrier is formed by conducting high-temperature heat treatment on conductive carbon black and nitrogen-containing organic matters; the transition metal atom interacts with the N atom in the carbon support and is anchored to the carbon support surface in the form of a single atom. Transition metal elements in the monatomic catalyst provided by the invention are uniformly distributed on the surface of a carbon carrier in an atomic form; in the detection of glucose, the monatomic catalyst shows sensitivity and detection limit obviously superior to those of the original conductive carbon black by virtue of the high reactivity of the monatomic metal center. The improvement of the performance of the carbon-based material can reduce the dosage of the biological enzyme in practical application and reduce the production cost.
Drawings
FIG. 1 is a transmission and scanning electron microscope image of Fe monatomic, Co monatomic, Cu monatomic, and Mn monatomic catalysts prepared in examples 1-4 of the present invention;
FIG. 2 is a spherical aberration corrected high angle annular dark field scanning transmission electron microscope image of Fe monatomic, Co monatomic, Cu monatomic, and Mn monatomic catalysts prepared in examples 1-4 of the present invention;
FIG. 3 is a diagram of an apparatus and a diagram of a monatomic catalyst prepared in examples 1 to 4 of the present invention;
FIG. 4 is a graph comparing the performance of monatomic catalysts prepared in examples 1-4 according to the present invention with that of virgin conductive carbon black for detecting hydrogen peroxide;
FIG. 5 is a graph comparing performance of monatomic catalysts prepared in examples 1-4 of the present invention with that of raw conductive carbon black for detecting glucose;
FIG. 6 is a graph comparing the performance of Fe monatomic catalyst prepared in example 1 according to the present invention and the performance of the original conductive carbon black in detecting glucose at different enzyme amounts.
Detailed Description
The invention provides a monatomic 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 nitrogen-containing 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 a single atom.
Wherein the conductive carbon black is one selected from KJ600, BP2000, XC72, and N326.
The nitrogen-containing organic matter is selected from one of 2,2' -bipyridyl, 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 the pyrolysis of the nitrogen-containing organic matter can be combined with metal atoms at a higher temperature to form an M-Nx structure, 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 monatomic 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 monatomic catalyst.
The invention firstly mixes the conductive carbon black, the transition metal compound and the solvent to obtain the mixed dispersion liquid.
Specifically, the mixing method is not particularly limited, and the conductive carbon black and the transition metal compound may be dispersed in the solvent separately.
Namely, dispersing conductive carbon black in a solvent to obtain a dispersion liquid of the conductive carbon black;
the transition metal compound is dispersed in a solvent to obtain a transition metal compound solution. Wherein, in the transition metal compound solution, the concentration of the transition metal compound is 0.3-1.0 mg/mL, preferably any value between 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 0.3-1.0 mg/mL. Wherein the transition metal compound is selected from one of ferric chloride 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 the application is not particularly limited, and in a specific embodiment, the drying is performed by spin-evaporating at 50-60 ℃ to remove the solvent.
And mixing the solid powder with the nitrogen-containing organic matter and calcining the mixture 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 effectively anchoring the metal elements on the surface of the carbon carrier in a form of single atoms.
The calcination is carried out in an inert atmosphere, the temperature is 800-900 ℃, preferably 800, 820, 840, 860, 880, 900, or any value between 800-900 ℃, and the time is 1-2 h, preferably 1, 1.5, 2, or 1-2 h; in a specific embodiment, the inert atmosphere is argon.
The application also provides an application of the monatomic catalyst, in particular to an application of the monatomic catalyst in the aspect of glucose content detection.
The application of the monatomic catalyst means that the monatomic 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 a generated current signal and the concentration of glucose present a certain linear relation. The application can be further used for manufacturing electrochemical test paper, flexible electrodes and the like. In specific embodiments of the present application, the monatomic 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 monatomic catalyst.
The invention also provides a flexible electrode for detecting glucose, which comprises the monatomic catalyst.
The preparation method of the monatomic catalyst provided by the invention is simple and easy to implement, and can be used for batch production, and reference is made to fig. 3, and fig. 3 is a device diagram and a material diagram for carrying out macro preparation on the monatomic 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 monatomic catalyst provided by the invention has great application potential in biosensing and has a high-efficiency detection function on glucose. The invention is suitable for the production of products such as electrochemical test paper, flexible electrodes and the like, can greatly reduce the dosage of biological enzyme in actual detection, and effectively reduces the cost.
In order to further understand the present invention, the monatomic catalyst applied to the sensing electrode, the preparation method thereof 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 monatomic catalyst:
(1) dispersing 100mg of conductive carbon black in 90mL of water, and carrying out ultrasonic treatment for 30 min; 10mL of ferric chloride hexahydrate aqueous solution of 0.5mg/mL is prepared; then mixing the two solutions, and stirring for more than 6 hours;
(2) carrying out rotary evaporation on the obtained mixed solution at 50-60 ℃ to completely volatilize the solvent to obtain Fe-C solid powder;
(3) mixing the obtained Fe-C solid powder with 500mg of melamine, and grinding for 1 h;
(4) putting the obtained solid powder into a porcelain boat, then putting the porcelain boat into a tubular furnace, sealing and introducing inert gas, heating to 900 ℃ under inert atmosphere, calcining for 1h, naturally cooling to room temperature, taking out to obtain the Fe monatomic catalyst, wherein the shape of the material is shown in figure 1; as shown in fig. 2, it was observed under a transmission electron microscope for spherical aberration correction that Fe single atoms were uniformly distributed on the nitrogen-doped carbon carrier.
FIG. 1 is a transmission and scanning electron microscope image of Fe monatomic, Co monatomic, Cu monatomic, and Mn monatomic catalysts prepared in examples 1 to 4 of the present invention. In FIG. 1, a corresponds to a Fe monatomic catalyst, b corresponds to a Co monatomic catalyst, c corresponds to a Cu monatomic catalyst, and d corresponds to a Mn monatomic catalyst.
FIG. 2 is a spherical aberration corrected high angle annular dark field scanning transmission electron microscope image of Fe monatomic, Co monatomic, Cu monatomic, and Mn monatomic catalysts prepared in examples 1-4 of the present invention. In FIG. 2, a corresponds to a Fe monatomic catalyst, b corresponds to a Co monatomic catalyst, c corresponds to a Cu monatomic catalyst, and d corresponds to a Mn monatomic catalyst.
Example 2
Preparation of Co monatomic catalyst:
(1) dispersing 100mg of conductive carbon black in 90mL of water, and carrying out ultrasonic treatment for 30 min; preparing 10mL of 1.0mg/mL cobalt nitrate hexahydrate aqueous solution; then mixing the two solutions, and stirring for more than 6 hours;
(2) performing rotary evaporation on the obtained mixed solution at 50-60 ℃ to completely volatilize the solvent to obtain Co-C solid powder;
(3) mixing the obtained Co-C solid powder with 100mg of 2,2' -bipyridine, and grinding for 1 h;
(4) putting the obtained solid powder into a porcelain boat, then putting the porcelain boat into a tube furnace, sealing and introducing inert gas, heating to 800 ℃ under the inert atmosphere, calcining for 2h, naturally cooling to room temperature, and taking out to obtain a Co monatomic catalyst, wherein the morphology of the material is shown in the attached figure 1; as shown in fig. 2, it was observed under a transmission electron microscope for spherical aberration correction that the Co single atoms were uniformly distributed on the nitrogen-doped carbon support.
Example 3
Preparation of Cu monatomic catalyst:
(1) dispersing 100mg of conductive carbon black in 90mL of water, and carrying out ultrasonic treatment for 30 min; preparing 10mL of 0.3mg/mL copper chloride dihydrate aqueous solution; then mixing the two solutions, and stirring for more than 6 hours;
(2) carrying out rotary evaporation on the obtained mixed solution at 50-60 ℃ to completely volatilize the solvent to obtain Cu-C solid powder;
(3) mixing the obtained Cu-C solid powder with 500mg of melamine, and grinding for 1 h;
(4) putting the obtained solid powder into a porcelain boat, then putting 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, taking out to obtain the Cu monatomic catalyst, wherein the material morphology is shown in figure 1; as shown in fig. 2, it was observed under a transmission electron microscope for spherical aberration correction that Cu single atoms were uniformly distributed on the nitrogen-doped carbon carrier.
Example 4
Preparation of Mn monatomic catalyst:
(1) dispersing 100mg of conductive carbon black in 90mL of water, and carrying out ultrasonic treatment for 30 min; preparing 10mL of 0.5mg/mL manganese chloride tetrahydrate aqueous solution; then mixing the two solutions, and stirring for more than 6 hours;
(2) rotationally evaporating the obtained mixed solution at 50-60 ℃ to completely volatilize the solvent to obtain Mn-C solid powder;
(3) mixing the obtained Mn-C solid powder with 500mg of melamine, and grinding for 1 h;
(4) putting the obtained solid powder into a porcelain boat, then putting the porcelain boat into a tubular 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 monatomic catalyst, wherein the morphology of the material is shown in the attached figure 1; as shown in fig. 2, it was observed under a transmission electron microscope for spherical aberration correction that Mn monoatomic atoms were uniformly distributed on the nitrogen-doped carbon carrier.
Example 5
Glucose sensing performance tests were performed on the Fe, Co, Cu, Mn monatomic catalysts prepared in examples 1 to 4:
(1) hydrogen peroxide sensing performance was evaluated by dropping 10 μ L of a catalyst dispersion (a) consisting of a monoatomic catalyst of 2mg/mL, ethanol/water (v/v ═ 1:1), and Nafion of 10 μ L/mL onto a clean glassy carbon electrode as a working electrode. A three-electrode system is utilized for testing, the reference electrode is an Ag/AgCl electrode, the counter electrode is a Pt wire, and the electrolyte is 1 multiplied by PBS buffer solution. The hydrogen peroxide sensing performance of the monatomic catalyst prepared in examples 1-4 is compared with that of original conductive carbon black, and the hydrogen peroxide sensing performance is shown in the attached figure 4; FIG. 4 is a graph comparing the performance of monatomic catalysts prepared in examples 1-4 according to the present invention with that of virgin conductive carbon black in detecting hydrogen peroxide. In FIG. 4, Fe 1 CN represents a Fe monatomic catalyst, Cu 1 CN represents a Cu monatomic catalyst, Co 1 CN represents a Co monoatomic catalyst, Mn 1 CN represents Mn monatomic catalyst, C represents original conductive carbon black, in the figure 4, a is a graph of continuous ampere-time response curve of the electrode modified by each catalyst to hydrogen peroxide, and b is a graph of the relationship between current response and hydrogen peroxide concentration obtained according to the result of the graph a. It can be seen that the monatomic catalyst has higher sensitivity, with the Fe monatomic catalyst having the best detection effect, since the high activity of the monatomic metal center further promotes the oxidation reaction of hydrogen peroxide.
(2)15 mu L of catalyst dispersion liquid (B) is dripped on a clean glassy carbon electrode to be used as a working electrode to evaluate the glucose sensing performance of the electrode, wherein the catalyst dispersion liquid (B) consists of 2mg/mL of monoatomic catalyst (500 mu L), glucose oxidase (1mL) and Nafion (50 mu L), and the enzyme amount on the electrode is 0.02-0.2U. The test is carried out by utilizing a three-electrode system, wherein the reference electrode is an Ag/AgCl electrode, the counter electrode is a Pt wire, and the electrolyte is 1 multiplied by PBS buffer solution. The comparison of the glucose sensing performance of the monatomic catalyst prepared in examples 1 to 4 with that of the original conductive carbon black is shown in fig. 5, and fig. 5 is a comparison graph of the performance of the monatomic catalyst prepared in examples 1 to 4 with that of the original conductive carbon black for detecting glucose, namely a relationship curve between the current response of the electrode modified by each catalyst to glucose and the glucose concentration. In FIG. 5, Fe 1 CN-0.2U represents that Fe monatomic catalyst and 0.2U enzyme are dripped on the working electrode, Cu 1 CN-0.2U represents that Cu monatomic catalyst and 0.2U enzyme are dripped on the working electrode, Co 1 CN-0.2U represents that Co single atom catalyst and 0.2U enzyme are dripped on the working electrode, Mn 1 CN-0.2U represents that Mn monatomic catalyst and 0.2U enzyme are dripped on the working electrode, and C-0.2U represents that original conductive carbon black and 0.2U enzyme are dripped on the working electrode. It can be seen from fig. 5 that the monatomic catalyst has superior sensitivity. FIG. 6 is a graph comparing the performance of Fe monatomic catalyst prepared in example 1 according to the present invention and the performance of the original conductive carbon black in detecting glucose at different enzyme amounts. In FIG. 6, Fe 1 CN-0.2U represents that Fe monatomic catalyst and 0.2U enzyme are dripped on the working electrode, Fe 1 CN-0.04U represents that Fe monatomic catalyst and 0.04U enzyme are dripped on the working electrode, Fe 1 CN-0.02U represents that Fe monatomic catalyst and 0.02U enzyme are dripped on the working electrode, C-0.2U represents that original conductive carbon black and 0.2U enzyme are dripped on the working electrode, a in figure 6 shows that the continuous ampere-time response curve of the Fe monatomic catalyst and the original conductive carbon black to glucose under different enzyme amounts respectively, b shows that the detection limit of the Fe monatomic catalyst and the original conductive carbon black to glucose is measured under 0.2U enzyme amount respectively, and C shows the relationship curve between the current response and the glucose concentration obtained according to the result of the a. As shown in FIG. 6, the Fe monatomic catalyst not only has a lower detection limit, but also has a lower detection limit when Fe monatomic catalyst is presentThe result shows that the introduction of the monatomic catalyst can greatly reduce the use of enzyme in glucose sensing, is beneficial to controlling the cost and improving the stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A monatomic catalyst applied to a sensing electrode is characterized by consisting of a carbon carrier and transition metal atoms, wherein the carbon carrier is formed by conducting carbon black and nitrogen-containing organic matters after 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 a single atom.
2. The monatomic catalyst of claim 1 wherein said 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' -bipyridyl, melamine, phenanthroline and urea;
the transition metal element is selected from one of Fe, Co, Cu and Mn.
3. The monatomic catalyst according to claim 1, wherein the mass ratio of the conductive carbon black to the nitrogen-containing organic substance is 1 (1-5);
the mass ratio of the transition metal atoms to the conductive carbon black is (1-2): 100.
4. A method for preparing the monatomic catalyst according to any one of claims 1 to 3, which comprises the steps of:
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 monatomic catalyst.
5. The method according to claim 4, wherein the transition metal compound is one selected from the group consisting of ferric chloride hexahydrate, cobalt nitrate hexahydrate, copper chloride dihydrate and manganese chloride tetrahydrate.
6. The method according to claim 4, wherein the solvent is water or ethanol.
7. The preparation method according to claim 4, wherein the calcination is carried out in an inert atmosphere at a temperature of 800 to 900 ℃ for 1 to 2 hours.
8. Use of a monatomic catalyst of any of claims 1-3 in glucose testing.
9. An electrochemical test strip for detecting glucose, comprising the monatomic catalyst according to any one of claims 1 to 3.
10. A flexible electrode for detecting glucose, comprising the monatomic catalyst of any one of claims 1 to 3.
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