CN114797843A - Carbon-supported metal nanocluster catalyst and preparation method and application thereof - Google Patents

Carbon-supported metal nanocluster catalyst and preparation method and application thereof Download PDF

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CN114797843A
CN114797843A CN202210316852.6A CN202210316852A CN114797843A CN 114797843 A CN114797843 A CN 114797843A CN 202210316852 A CN202210316852 A CN 202210316852A CN 114797843 A CN114797843 A CN 114797843A
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metal
catalyst
carbon
nanocluster
salt
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吴敏芳
李良
高猛
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Advanced Institute of Information Technology AIIT of Peking University
Hangzhou Weiming Information Technology Co Ltd
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Advanced Institute of Information Technology AIIT of Peking University
Hangzhou Weiming Information Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B01J35/40—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/32—Freeze drying, i.e. lyophilisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • 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
    • 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
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • 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
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
    • 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

Abstract

The invention relates to a preparation method of a carbon-supported metal nanocluster catalyst, which comprises the steps of firstly mixing a metal salt solution containing a metal chelate and a nitrogen source with a carbon material, freeze-drying and roasting to form a pre-catalyst, then combining the pre-catalyst with a working electrode and putting the pre-catalyst into electrolyte containing a guiding agent, and carrying out electrochemical oxidation reduction treatment on the pre-catalyst by a cyclic voltammetry method to obtain the stable metal nanocluster catalyst. The pre-catalyst is treated by cyclic voltammetry, so that the supported metal nanoclusters are distributed more uniformly, and the agglomeration phenomenon is reduced. In the electrochemical oxidation-reduction treatment process, the guiding agent can guide the supported metal to reconstruct the exposed crystal face, so that the exposure proportion of the crystal face with catalytic activity is increased, and the catalytic performance is improved. The metal nanocluster catalyst disclosed by the invention has an ultra-small size and good biocompatibility, is beneficial to being safely discharged by organisms, and has a good application prospect in the field of biosensing.

Description

Carbon-supported metal nanocluster catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to a carbon-supported metal nanocluster catalyst and a preparation method and application thereof.
Background
Metal Nanoclusters (MNCs) are a new class of functional nanomaterials consisting of several to several hundred atoms of the same or different species, with dimensions within 2nm, with properties not found for a single atom or bulk material. On one hand, the ultra-small size of the metal nanoclusters increases the proportion of surface atoms, and shows an excellent surface structure and rich active sites; on the other hand, the metal cluster is close to the de broglie wavelength, and the continuous electronic energy band thereof can evolve into discrete energy levels, thereby showing the property similar to a metal complex. And further, the catalyst shows unique catalytic properties, so that the catalytic activity can be improved. However, the existing metal nanocluster catalyst generally has the defects of poor metal nanocluster dispersibility and easy agglomeration, so that the catalytic performance of the catalyst is low.
Therefore, it is required to develop a method for preparing a metal nanocluster catalyst that allows the metal nanoclusters to be uniformly distributed without agglomeration and with improved catalytic performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a carbon-supported metal nanocluster catalyst, which comprises the steps of firstly mixing a metal salt solution containing a metal chelate and a nitrogen source with a carbon material, freeze-drying and roasting to form a pre-catalyst, then combining the pre-catalyst with a working electrode, putting the pre-catalyst into an electrolyte containing a guiding agent, and carrying out electrochemical oxidation reduction treatment on the pre-catalyst by a cyclic voltammetry method to obtain the stable metal nanocluster catalyst. The pre-catalyst is treated by cyclic voltammetry, so that the supported metal nanoclusters are distributed more uniformly, and the agglomeration phenomenon is reduced. In addition, in the electrochemical oxidation-reduction treatment process, the guiding agent can guide the supported metal to reconstruct an exposed crystal face, so that the exposure proportion of the crystal face with catalytic activity is increased, and the catalytic performance is improved.
It is another object of the present invention to provide a carbon-supported metal nanocluster catalyst having a large specific surface area and a large number of active sites, thus having excellent catalytic performance, obtained by the preparation method.
The metal nanocluster catalyst has an ultra-small size and good biocompatibility, so that the metal nanocluster catalyst is beneficial to being safely discharged by organisms, and has a good application prospect in the field of biosensing. Therefore, it is still another object of the present invention to provide a biosensor using the carbon-supported metal nanocluster catalyst.
It is still another object of the present invention to provide the biosensor for detecting H 2 O 2 Concentration or concentration of biomolecules such as blood glucose, galactose, cholesterol, amino acids, alcohols, lactic acid or uric acid.
In order to achieve the above object, the present invention provides the following technical solutions.
A method of preparing a carbon-supported metal nanocluster catalyst, comprising:
preparing a metal salt solution, wherein the metal salt solution comprises a metal salt, a metal chelate, a nitrogen source and a solvent;
mixing the metal salt solution with a carbon material and freeze-drying to obtain a freeze-dried sample;
roasting the freeze-dried sample in an inert atmosphere to obtain a carbon-supported metal nanocluster pre-catalyst; and
and combining the metal nanocluster precatalyst with a working electrode, putting the combined metal nanocluster precatalyst into electrolyte containing a guiding agent, and carrying out electrochemical oxidation reduction treatment on the metal nanocluster precatalyst through cyclic voltammetry to obtain the stable metal nanocluster catalyst, wherein the guiding agent is a target product of a reaction which can be catalyzed by the metal nanocluster catalyst.
Preferably, the metal salt may be one or more of Pt salt, Au salt, Ag salt, Ir salt, Pd salt and Rh salt. More preferably, the metal salt may be H 2 PtCl 6 ·xH 2 O、AuCl、AgNO 3 、IrCl 3 ·3H 2 O、PdCl 2 、RhCl 3 ·3H 2 One or more of O.
Preferably, the metal chelate is a saccharide such as glucose. The metal chelate compound can play a role in physically separating metal ions, so that metal nanoclusters in the catalyst are uniformly distributed on the surface of a carbon carrier without agglomeration, and high dispersity of the metal nanoclusters is maintained. The metal chelate can also be bound to an oxygen-rich carbon support through the interaction of oxygen-containing functional groups. In addition, the catalyst can be decomposed after being calcined, and the catalyst does not remain, so that the catalytic performance of the catalyst is not influenced.
Preferably, the nitrogen source is one or more of melamine, dicyandiamide and urea. The nitrogen source can play an anchoring role, and the uniformly distributed metal nanoclusters can be anchored on the surface of the carbon carrier at high temperature through the combination of N atoms modified on the surface of the carbon carrier and metal ions in the metal salt, so that the metal nanoclusters do not move or agglomerate in the using process, and the high dispersibility of the metal nanoclusters is kept.
Preferably, the solvent is water, or a mixture of water and alcohols. More preferably, the solvent is a mixture of water and alcohols. The alcohols can eliminate the surface tension of the carbon material, so that the carbon material can be uniformly dispersed in the solvent together with other substances. Of course, the solvent of the present invention may also be any other solvent capable of dissolving the metal salt, the metal chelate compound and the nitrogen source.
Preferably, the molar ratio of the metal salt, the metal chelate compound and the nitrogen source calculated as the molar amount of the metal atom is 1 (1-5): 5-30, preferably 1 (1-5): 10-20. If the metal salt ratio is too small, the active sites are too small, the catalytic performance is not obvious, and the whole carbon material has the performance of the carbon material. When the metal salt content is too much, the size of the metal particles is larger than 2nm and is not cluster any more, so that the atom utilization rate is relatively reduced, the number of catalytically active sites is reduced, and although the amount is increased, the catalytic performance is not increased and is reduced, and unnecessary waste of precious metals is caused.
Preferably, the method for preparing the metal salt solution comprises the following steps: preparing a metal chelate aqueous solution and a nitrogen source aqueous solution from a metal chelate and a nitrogen source respectively; adding metal salt into the metal chelate aqueous solution at the temperature of 20-30 ℃; after stirring, the nitrogen source aqueous solution was added and stirring was continued to obtain a metal salt solution. The method for preparing the metal salt solution of the invention is beneficial to the dispersion of the metal, and the following conditions can occur when all the components are mixed and stirred together: the metal salt solution is not uniformly dispersed, and even the situation of local complexation can occur, which is not beneficial to the dispersion of the metal.
Preferably, the carbon material is one or more of carbon nanoparticles, conductive carbon black, lamp black carbon, carbon fibers, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene fibers, two-dimensional graphene paper, three-dimensional carbon foam, and three-dimensional graphene aerogel. Preferably, the carbon material is one or more of a single-walled carbon nanotube and a multi-walled carbon nanotube. The carbon nano tube can penetrate through protein wrapped outside the enzyme and directly contacts with an active center prosthetic group of the enzyme, namely, an electron mediator is not needed, so that the enzymatic reaction is favorably carried out, the reaction is not limited by dissolved oxygen in a solution, and the potential required by the sensor can be reduced to a certain extent (after the working potential is reduced, the anti-interference capability of the sensor is enhanced). Preferably, the carbon material is modified with N atoms or S atoms. The modified carbon material can enable the metal nanoclusters to be stably dispersed on the carbon material. The carbon material has the advantages of low cost, high conductivity, easy modification and the like, and the carbon material is used as the carrier of the metal nanocluster, so that the cost can be reduced, and the enzyme can be captured and surrounded at the same time to a certain extent, thereby strengthening the fixation of the enzyme in a sensor which needs to combine the catalyst and the enzyme for use, and improving the stability of the product. In addition, the carbon material may also function to some extent as a tamper resistant layer and a "mediator-free" electron transport layer.
Preferably, sonication is performed after mixing the metal salt solution with the carbon material and before freeze-drying. The ultrasound time is preferably 1 to 3 hours. The ultrasonic power is preferably 60-150W. After freeze-drying, the solvent was completely removed.
Preferably, the inert atmosphere may be argon, nitrogen, helium or a mixture thereof.
Preferably, the calcination temperature may be 400 ℃ to 800 ℃, preferably 500 ℃ to 600 ℃. Too high a calcination temperature can cause the formation of metal particles with larger sizes, so that the proportion of surface atoms is reduced, the reactive sites are reduced, and the catalytic performance of the catalyst is reduced; in addition, too high a calcination temperature allows direct sublimation of the nitrogen source, resulting in a reduction in the amount of the nitrogen source in the catalyst. In addition, the pipeline can be plugged up in the terminal condensation of pipeline to sublimed nitrogen source, and then brings danger for the experiment. Too low a firing temperature results in too long a firing time required, increasing time costs. In addition, too low a temperature can result in incomplete pyrolysis of the glucose or nitrogen source. If the glucose remains, the detection result of the glucose sensor at the later stage is affected. If the nitrogen source is not pyrolyzed completely, the anchoring effect of the metal is affected.
Preferably, the heating rate is 1-5 ℃/min, preferably 1-3 ℃/min. Too fast temperature rise can cause temperature runaway to bring potential safety hazards to the experiment, and metal sintering can also be carried out. Too slow a temperature rise requires too long a time, increasing time costs, and in addition, long exposure to high temperatures can cause an increase in metal particles.
Preferably, the calcination time may be 2 to 6 hours, preferably 3 to 5 hours.
Preferably, the directing agent may be O 2 、H 2 、CO、CH 4 、H 2 O 2 Sodium nitrite, formic acid or acetic acid, and the like. The guiding agent of the present invention is not limited to these, and any guiding agent may be used as long as it is a target product of a reaction that can be catalyzed by the metal nanocluster catalyst. The guiding agent used may be determined according to the catalytic target of the metal nanocluster catalyst, for example, O may be utilized when the metal nanocluster catalyst is used to catalyze an oxidation reaction in which hydrogen peroxide participates 2 The prepared pre-catalyst is used as a guiding agent to carry out electrochemical oxidation reduction treatment, and the prepared catalyst has excellent catalytic performance on oxidation reaction in which hydrogen peroxide participates.
In the present invention, the expression "a reaction capable of being catalyzed by the metal nanocluster catalyst" is understood to mean a chemical reaction that is carried out under the action of the metal nanocluster catalyst. The target product of the chemical reaction may be a gas, a liquid, or a solid. The target product is a directing agent for the electrochemical redox treatment of the invention. For example, when the concentration of hydrogen peroxide is detected by the metal nanocluster catalyst, the oxidation product of the hydrogen peroxide is electrically catalyzed to O 2 Thus, during said electrochemical redox treatment, with O 2 As a directing agent. In the electrochemical oxidation-reduction treatment process, the guiding agent can guide the supported metal to reconstruct the exposed crystal face, so that the exposure proportion of the crystal face with catalytic activity is increased, and the catalytic performance is improved. And the crystal faces of the metal nanocluster pre-catalyst which is not subjected to electrochemical oxidation reduction treatment are arranged in a disordered way, so that the crystal faces with catalytic activity are exposed to a small proportion, and the catalytic activity is low.
Preferably, when the guiding agent is a gas (e.g. O) 2 ) Firstly, introducing a gas guiding agent into the electrolyte to saturate the electrolyte, and preferably, introducing the gas for 30-60 min; then carrying out electrochemical oxidation-reduction treatment under the condition of continuously introducing the gas guiding agent. Preferably, the rate at which the gas guiding agent is introducedThe ratio may be 1ml/min to 200ml/min, preferably 10 to 100 ml/min. The gas guiding agent is in a saturated state in the electrolyte, so that the dissolving amount of gas components is maximized on one hand, and the dissolving amount of the gas in the electrolyte is convenient to control to be constant on the other hand, thereby enabling the repeated preparation of the catalyst.
Preferably, when the guiding agent is a liquid or a solid, the concentration thereof in the electrolyte may be 20 mM-1M, preferably 50 mM-0.2M.
Preferably, the scanning speed of the electrochemical oxidation-reduction treatment is 10-200 mV/s, preferably 50-100 mV/s. Preferably, the scanning potential window is-5V, preferably-4V. Preferably, the number of scanning times is 1 to 500, preferably 50 to 200.
In the present invention, the metal nanocluster catalyst obtained after the electrochemical redox treatment may be directly used for detecting H since it is already supported on the working electrode 2 O 2 Concentration or biomolecule concentration.
Alternatively, the resulting metal nanocluster catalyst may be removed from the working electrode for use in a catalytic reaction.
The present invention also provides a carbon-supported metal nanocluster catalyst obtained by the preparation method. The metal nanoclusters in the catalyst of the present invention are uniformly distributed on the carbon support, and the particle size may be 0.5 to 2nm, preferably 0.9 to 1.9 nm. Preferably, the content of the metal element is 0.5 to 15 wt%, preferably 0.5 to 10 wt%, based on the total mass of the metal nanocluster catalyst.
The metal nanocluster catalyst of the present invention can reduce an overpotential required for a hydrogen peroxide oxidation reaction.
The metal nanoclusters of the invention can be uniformly and stably distributed on the carbon carrier, and have large surface atomic ratio and more reactive active sites, so that the dosage of the catalyst can be reduced, and the dosage of metal elements can be correspondingly reduced, thereby greatly reducing the cost.
The present invention also provides a biosensor using the carbon-supported metal nanocluster catalyst.
In a first preferred embodiment of the present invention, the biosensor comprises:
a base layer;
the working electrode is arranged on the surface of the substrate layer; and
an electrocatalytic layer disposed on a surface of the working electrode and including the carbon-supported metal nanocluster catalyst.
Preferably, the substrate layer may be polyimide, polytetrafluoroethylene, polyethylene, polyvinyl chloride, polypropylene, polycarbonate, polyimide, polyethylene terephthalate, acrylonitrile-butadiene-styrene polymer, or polymethyl methacrylate.
Preferably, the electrocatalytic layer is formed by a Nafion solution dispersion method, a screen printing method, an embedding method, or a covalent bonding method.
The biosensor of the first preferred embodiment can be used to detect H 2 O 2 And (4) concentration.
In the organism, H 2 O 2 Can be used as active oxygen substance, and is involved in various physiological and pathological processes of cell proliferation, differentiation and migration; can be used as one of the most important signals of oxidative stress, such as H in urine 2 O 2 The concentration can be used as index of whole body oxidative stress, and can be used for regulating renal function and diagnosing various diseases. In addition, H 2 O 2 Is a key byproduct of a plurality of enzymatic reactions in vivo, such as enzymatic reactions involving glucose oxidase, cholesterol oxidase or lactate oxidase, and the like. Thus, H in the nM and μ M range 2 O 2 The sensitivity detection of (2) is very important for the biomedical fields of health monitoring, disease diagnosis and the like. The biosensor of the present invention uses the carbon-supported metal nanocluster catalyst, and thus the sensitivity, detection limit, and linear response range of the biosensor are significantly improved.
In addition, existing for H 2 O 2 The catalytic catalyst generally comprises a high loading of noble metal material, which, due to its high cost, can be applied to biosensors, and can impose a heavy economic burden on the patient. While the metal nanoclusters of the present inventionThe catalyst only contains low-load precious metals, and the main component of the catalyst is a carbon material with low cost, so that the manufacturing cost of the biosensor is greatly reduced. In addition, the carbon material supporting metal nanoclusters in the present invention can be used not only as a carrier for metal nanoclusters but also as a carrier for H 2 O 2 Also has certain catalytic activity.
In a second preferred embodiment of the present invention, the biosensor comprises:
a base layer;
the working electrode is arranged on the surface of the substrate layer;
an electrocatalytic layer disposed on a surface of the working electrode and comprising the carbon-supported metal nanocluster catalyst; and
the biological catalysis layer is arranged on the surface of the electric catalysis layer and comprises biological enzymes.
Preferably, the biological enzyme is glucose oxidase, galactose oxidase, cholesterol oxidase, amino acid oxidase, alcohol oxidase, lactate oxidase, uricase, or the like.
Preferably, the biocatalytic layer is formed by an entrapment method, an adsorption method, a covalent bonding method or a crosslinking method.
Preferably, the biosensor further comprises: the macromolecule layer is arranged on the surface of the biological catalytic layer.
Preferably, the polymer layer may be polydimethylsiloxane, polyurethane, cellulose acetate, polycarbonate, polyurea cellulose acetate, Nafion, polyester sulfonic acid, polyvinyl alcohol, polyethylene glycol, polyurethane, polytetrafluoroethylene, polyvinyl chloride, or the like. The provision of a polymer layer has the following advantages: larger molecules such as protein can be prevented from diffusing into the catalyst layer, so that the interference on the electrode is reduced; regulating the proportion of glucose and oxygen entering the biological catalytic layer; the loss of the biological catalytic layer enzyme is prevented; and improving the biocompatibility of the sensor.
The biosensor of the second preferred embodiment may be used to detect the concentration of biomolecules, such as blood glucose, galactose, cholesterol, amino acids, alcohols, lactic acid, or uric acid, because it includes a bio-catalytic layer.
The carbon material can be used as a carrier of the metal nanocluster and a carrier of biological enzyme, is beneficial to enhancing the fixation of the enzyme, improving the load capacity of the biological enzyme, improving the contact degree of the enzyme and the metal cluster catalyst and prolonging the effective period of the enzyme activity, thereby prolonging the service life of the biosensor.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of a carbon-supported metal nanocluster catalyst, which comprises the steps of firstly mixing a metal salt solution containing a metal chelate and a nitrogen source with a carbon material, freeze-drying and roasting to form a pre-catalyst, then combining the pre-catalyst with a working electrode, putting the pre-catalyst into electrolyte containing a guiding agent, and carrying out electrochemical oxidation reduction treatment on the pre-catalyst by a cyclic voltammetry method, thereby obtaining the stable metal nanocluster catalyst. The pre-catalyst is treated by cyclic voltammetry, so that the supported metal nanoclusters are distributed more uniformly, and the agglomeration phenomenon is reduced. In addition, in the electrochemical oxidation-reduction treatment process, the guiding agent can guide the supported metal to reconstruct an exposed crystal face, so that the exposure proportion of the crystal face with catalytic activity is increased, and the catalytic performance is improved.
In addition, the electrochemical oxidation-reduction treatment of the invention can stabilize the catalytic performance of the electrode and provide guarantee for the commercial application of the subsequent electrode.
In addition, the preparation method of the metal nanocluster catalyst is simple and repeatable.
2. The metal nanocluster catalyst has large specific surface area and many active sites, so that the metal nanocluster catalyst has excellent catalytic performance, can be used for preparing a hydrogen peroxide sensor, a blood glucose sensor and the like, and is wide in application range.
3. The preparation process of the biosensor has repeatability, equipment and raw materials are easy to obtain, the consistency of the catalytic performance of the sensor is easy to realize, and the preparation process is also favorable for batch production.
Drawings
FIG. 1 is a high angle annular dark field scanning Transmission Electron Microscope (TEM) image of a Pt NCs2 sample prepared in example 2.
FIG. 2 is a graph of the current density over time obtained using the hydrogen peroxide biosensor of example 5.
FIG. 3 is a graph of hydrogen peroxide concentration versus response current density obtained using the hydrogen peroxide biosensor of example 5.
Detailed Description
In order to facilitate understanding of the present invention, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention. Unless otherwise indicated, the starting materials and reagents used in the examples are all commercially available products. Reagents, equipment, or procedures not described herein are routinely determinable by one of ordinary skill in the art.
Example 1: preparation of Pt nanocluster catalyst Pt NCs1
1g of conductive carbon black material and 26.5mg of chloroplatinic acid hexahydrate (H) were weighed 2 PtCl 6 ·6H 2 O), 9.3mg glucose and 10.77mg melamine (chloroplatinic acid hexahydrate calculated as the molar amount of platinum atoms, glucose and melamine calculated as the molar amount of nitrogen atoms in a molar ratio of 1:1: 10). Glucose was dissolved in 30mL of deionized water to prepare an aqueous glucose solution, and melamine was dissolved in 30mL of deionized water to prepare an aqueous melamine solution. Adding chloroplatinic acid hexahydrate into the glucose aqueous solution, reacting for 0.5h, then adding a melamine aqueous solution, and continuing to react for 0.5 h. Then, conductive carbon black is added into the solution and is subjected to ultrasonic treatment for 100W for 1 h. Then freeze-dried to completely remove the deionized water. Finally, the sample was placed in a tube furnace at a flow rate of 100mL/min N 2 Heating to 500 ℃ at the speed of 2 ℃/min under the atmosphere, and keeping for 5h to obtain the pre-catalyst. The prepared pre-catalyst is combined with a working electrode and then connected by using a three-electrode system. In an electrolyte (phosphate buffer solution with pH 7.4,concentration of 30mM) was passed through O at a rate of 100ml/min 2 For 30min, adding O in the electrolyte 2 Saturation (electrocatalytic oxidation of hydrogen peroxide to O 2 Therefore, with O 2 As the treatment atmosphere for the present precatalyst). Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 50ml/min, the scanning speed is 50mV/s, the scanning times are 100 times, and the scanning range is-2V. After completion, Pt NCs1 was obtained.
TEM characterization showed that the particle size of the Pt nanoclusters supported on conductive carbon black was 0.9nm, and Inductively Coupled Plasma (ICP) analysis results showed that the Pt content in this sample was 0.89 wt%.
Example 2: preparation of Pt nanocluster catalyst Pt NCs2
1g of activated carbon nanoparticles, 0.13g of chloroplatinic acid hexahydrate, 0.23g of glucose and 80.81mg of dicyandiamide were weighed (the molar ratio of chloroplatinic acid hexahydrate, glucose and dicyandiamide, calculated as the molar amount of platinum atoms, was 1:5: 15). Dissolving glucose in 40mL of deionized water to prepare a glucose aqueous solution, and dissolving dicyandiamide in 30mL of deionized water to prepare a dicyandiamide aqueous solution. Adding chloroplatinic acid hexahydrate into the glucose aqueous solution, reacting for 1h, then adding dicyandiamide aqueous solution, and continuing to react for 1 h. Then, activated carbon nanoparticles are added into the solution, and the solution is subjected to ultrasonic treatment for 150W for 1 h. Followed by lyophilization to completely remove the deionized water. The sample was then placed in a tube furnace at a flow rate of 200mL/min N 2 Heating to 600 ℃ at the speed of 2 ℃/min under the atmosphere, and keeping for 3h to obtain the pre-catalyst. The prepared pre-catalyst is combined with a working electrode and then connected by using a three-electrode system. O was passed through an electrolyte (phosphate buffer solution at pH 7.4, 30mM) at a rate of 100ml/min 2 For 30min, adding O in the electrolyte 2 And (4) saturation. Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 10ml/min, the scanning frequency is 50 times at the scanning speed of 10mV/s, and the scanning range is-2V. After completion, Pt NCs2 was obtained.
Fig. 1 is a transmission electron micrograph of the obtained Pt NCs2 sample, from which it can be seen that Pt is a nanocluster particle uniformly distributed on activated carbon. The size of the Pt nanocluster particles supported on activated carbon was about 1.7nm by TEM data analysis. The ICP results show that the Pt content in this sample is 4.01 wt%.
Example 3: preparation of Au nanocluster catalyst Au NCs1
1g S doped carbon nanotube material, 82.60mg gold chloride (AuCl), 64.03mg glucose and 213.44mg urea were weighed (the molar ratio of gold chloride, glucose and urea calculated as gold atom molar mass was 1:1:20 calculated as nitrogen atom molar mass). Glucose was dissolved in 30mL of deionized water to prepare an aqueous glucose solution, and urea was dissolved in 20mL of deionized water to prepare an aqueous urea solution. Adding gold chloride into the glucose aqueous solution, reacting for 2h, then adding the urea aqueous solution, and continuing to react for 2 h. And then adding the S-doped carbon nanotube material into the solution, and carrying out ultrasonic treatment for 60W for 1 h. Followed by lyophilization to completely remove the deionized water. Then the sample was placed in a tube furnace, heated to 400 ℃ at a rate of 1 ℃/min under He atmosphere at a flow rate of 100mL/min, and held for 6 hours to obtain a precatalyst. The prepared pre-catalyst is combined with a working electrode and then connected by using a three-electrode system. O was passed through an electrolyte (phosphate buffer solution at pH 7.4, 30mM) at a rate of 100ml/min 2 For 30min, adding O in the electrolyte 2 And (4) saturation. Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 200ml/min, the scanning speed is 50mV/s, the scanning times are 200 times, and the scanning range is-3V. After completion, Au NCs1 was obtained.
TEM characterization showed the size of the supported Au nanocluster particles on the carbon nanotubes to be 1.8nm, and ICP results showed the Au content in this sample to be 6.12 wt%.
Example 4: preparation of Ir nanocluster catalyst Ir NCs1
Weighing 1g of graphene material and 0.28g of iridium chloride trihydrate (IrCl) 3 ·3H 2 O), 0.28g of glucose and 0.33g of melamine (the molar ratio of iridium chloride trihydrate, glucose and melamine calculated as the molar amount of iridium atoms is 1:2: 20). Dissolving glucose in 50mL deionized water to obtain grapeAn aqueous sugar solution, melamine was dissolved in 50mL of deionized water to prepare an aqueous melamine solution. Adding iridium chloride trihydrate into the glucose aqueous solution, reacting for 1 hour, then adding the melamine aqueous solution, and continuing to react for 1 hour. And then adding the graphene material into the solution, and carrying out ultrasonic treatment for 100W for 1 h. Followed by lyophilization to completely remove the deionized water. And then putting the sample into a tube furnace, heating to 800 ℃ at the speed of 3 ℃/min under the Ar atmosphere with the flow rate of 150mL/min, and keeping for 2h to obtain the pre-catalyst. The prepared pre-catalyst was combined with the working electrode and then connected using a three-electrode system. O was passed through an electrolyte (phosphate buffer solution at pH 7.4, 30mM) at a rate of 100ml/min 2 For 30min, adding O in the electrolyte 2 And (4) saturation. Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 200ml/min, the scanning frequency is 50 times at the scanning speed of 10mV/s, and the scanning range is-2V. After completion, Ir NCs1 was obtained.
The TEM characterization shows that the size of Ir nanocluster particles supported on graphene is 1.9nm, and the ICP result shows that the Ir content in the sample is 9.09 wt%.
Example 5: construction of Hydrogen peroxide biosensor
And modifying the working electrode by adopting a Nafion solution dispersion method. Prepare 0.5% nafion water solution. 20mg of the precatalyst of example 2, i.e. the Pt nanocluster catalyst, was weighed and added to 1mL of nafion aqueous solution, and then subjected to ultrasonic treatment for 30min to be uniformly distributed. The prepared slurry was applied to the surface of a working electrode in a three-electrode system in an amount of 1. mu.L using a pipette gun. The connection is then made using a three-electrode system. O was passed through an electrolyte (phosphate buffer solution at pH 7.4, 30mM) at a rate of 100ml/min 2 For 30min, adding O in the electrolyte 2 And (4) saturation. Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 10ml/min, the scanning frequency is 50 times at the scanning speed of 10mV/s, and the scanning range is-2V. And after finishing, washing with deionized water, and drying at 40 ℃ for later use.
And testing the response performance of the constructed electrode to the hydrogen peroxide. The test process is that Pt is used as a counter electrode, Ag/AgCl is used as a reference electrode, and the modified electrode is used as a working electrode to assemble a three-electrode system. The three-electrode system was placed in an electrolyte (30mM phosphate buffered solution, pH 7.4), an operating potential of 0.55V vs Ag/AgCl was applied, hydrogen peroxide was added at a certain concentration every 5min to increase the hydrogen peroxide concentration in the final solution in a gradient of 30 μ M, and the change in current density with the continuous addition of hydrogen peroxide was recorded by chronoamperometry, as shown in fig. 2.
The hydrogen peroxide concentration of figure 3 is plotted against the response current density using the data of figure 2. As can be seen from the figure, the curves satisfy a linear relationship at low substrate concentrations, i.e., 0 to 180. mu.M. The detection limit is 15.82 mu M (signal-to-noise ratio S/N is 3), and the detection range is 5 mu M-3600 mu M.
According to the same method, the working electrodes were modified with the metal cluster catalysts prepared in examples 1 to 4, respectively, to prepare hydrogen peroxide sensors, whose hydrogen peroxide detection performance is shown in table 1 below.
TABLE 1
Figure BDA0003570054760000171
Example 6: construction of blood glucose sensor
And modifying the working electrode by adopting a Nafion solution dispersion method. Prepare 0.5% nafion phosphate buffer solution. 20mg of the precatalyst of example 2, i.e. the Pt nanocluster catalyst, was weighed and added to 1mL of nafion phosphate buffer solution, and then evenly distributed by sonication for 30 min. The prepared slurry was taken out by 1 μ L with a pipette gun, coated on the surface of a working electrode in a three-electrode system, and then connected using the three-electrode system. Introducing O into the electrolyte at a rate of 100ml/min 2 For 30min, adding O in the electrolyte 2 And (4) saturation. Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 10ml/min, the scanning frequency is 50 times at the scanning speed of 10mV/s, and the scanning range is-2V. And after finishing, washing with deionized water, and drying at 40 ℃ for later use. The Pt NCs2 modified electrode was immersed in 5mg mL at 4 deg.C -1 Glucose oxidase in PBS buffer solution for 48h, washed with PBS solution, and stored at 4 ℃ for later use.
The working electrodes were modified with the metal cluster catalysts prepared in examples 1 to 4, respectively, to prepare blood glucose sensors whose glucose detection performance is shown in table 2 below.
TABLE 2
Figure BDA0003570054760000181
Comparative example 1: preparation of Pt nanocluster catalyst Pt NCs1-A
1g of conductive carbon black material, 26.5mg of chloroplatinic acid hexahydrate, and 10.77mg of melamine were weighed (the molar ratio of chloroplatinic acid hexahydrate, calculated as the molar amount of platinum atoms, to melamine, calculated as the molar amount of nitrogen atoms, was 1: 10). The melamine was dissolved in 60mL of deionized water to prepare an aqueous melamine solution. Adding chloroplatinic acid hexahydrate into a melamine aqueous solution, and reacting for 0.5 h. Then, conductive carbon black is added into the solution and is subjected to ultrasonic treatment for 100W for 1 h. Then freeze-dried to completely remove the deionized water. Finally, the sample was placed in a tube furnace at a flow rate of 100mL/min N 2 Heating to 500 ℃ at the speed of 2 ℃/min under the atmosphere, and keeping for 5h to obtain the pre-catalyst. The prepared pre-catalyst is combined with a working electrode and then connected by using a three-electrode system. O was passed through an electrolyte (phosphate buffer solution at pH 7.4, 30mM) at a rate of 100ml/min 2 For 30min, adding O in the electrolyte 2 Saturation (electrocatalytic oxidation of hydrogen peroxide to O 2 Therefore, with O 2 As the treatment atmosphere for the present precatalyst). Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 50ml/min, the scanning speed is 50mV/s, the scanning times are 100 times, and the scanning range is-2V. After completion, Pt NCs1-A was obtained.
The TEM characterization showed that the particle size of the Pt nanocluster supported on the conductive carbon black was 3.4nm, and the ICP analysis result showed that the Pt content in this sample was 0.87 wt%.
Comparative example 2: preparation of Pt nanocluster catalyst Pt NCs1-B
1g of conductive carbon black material, 26.5mg of chloroplatinic acid hexahydrate, and 9.3mg of glucose were weighed (molar ratio of chloroplatinic acid hexahydrate to glucose calculated as platinum atom molar weight was 1: 1). Glucose was dissolved in 60mL of deionized water to prepare an aqueous glucose solution. Chloroplatinic acid hexahydrate is added into the glucose aqueous solution and reacted for 0.5 h. Then, conductive carbon black is added into the solution and is subjected to ultrasonic treatment for 100W for 1 h. Then freeze-dried to completely remove the deionized water. Finally, the sample was placed in a tube furnace at a flow rate of 100mL/min N 2 Heating to 500 ℃ at the speed of 2 ℃/min under the atmosphere, and keeping for 5h to obtain the pre-catalyst. The prepared pre-catalyst is combined with a working electrode and then connected by using a three-electrode system. O was passed through an electrolyte (phosphate buffer solution at pH 7.4, 30mM) at a rate of 100ml/min 2 For 30min, adding O in the electrolyte 2 Saturation (electrocatalytic oxidation of hydrogen peroxide to O 2 Therefore, with O 2 As the treatment atmosphere for the present precatalyst). Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 50ml/min, the scanning speed is 50mV/s, the scanning times are 100 times, and the scanning range is-2V. After completion, Pt NCs1-B was obtained.
The TEM characterization showed that the particle size of the Pt nanoclusters supported on the conductive carbon black was 5.1nm, and the ICP analysis result showed that the Pt content in this sample was 0.91 wt%.
Comparative example 3: preparation of Pt nanocluster catalyst Pt NCs1-C
1g of conductive carbon black material and 26.5mg of chloroplatinic acid hexahydrate were weighed. Chloroplatinic acid hexahydrate was added to 60mL of deionized water. Then, conductive carbon black is added into the solution and is subjected to ultrasonic treatment for 100W for 1 h. Then freeze-dried to completely remove the deionized water. Finally, the sample was placed in a tube furnace at a flow rate of 100mL/min N 2 Heating to 500 ℃ at the speed of 2 ℃/min under the atmosphere, and keeping for 5h to obtain the pre-catalyst. The prepared pre-catalyst is combined with a working electrode and then connected by using a three-electrode system. O was passed through an electrolyte (phosphate buffer solution at pH 7.4, 30mM) at a rate of 100ml/min 2 For 30min, makeO in electrolyte 2 Saturation (electrocatalytic oxidation of hydrogen peroxide to O 2 Therefore, with O 2 As the treatment atmosphere for the present precatalyst). Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 50ml/min, the scanning speed is 50mV/s, the scanning times are 100 times, and the scanning range is-2V. After completion, Pt NCs1-C was obtained.
The TEM characterization showed that the particle size of the Pt nanoclusters supported on the conductive carbon black was 6.4nm, and the ICP analysis result showed that the Pt content in this sample was 0.83 wt%.
Comparative example 4: preparation of Pt nanocluster catalyst Pt NCs1-D
1g of conductive carbon black material, 26.5mg of chloroplatinic acid hexahydrate, 9.3mg of glucose and 1.1mg of melamine were weighed (the molar ratio of chloroplatinic acid hexahydrate calculated as the molar amount of platinum atoms, glucose and melamine calculated as the molar amount of nitrogen atoms was 1:1: 1). Glucose was dissolved in 30mL of deionized water to prepare an aqueous glucose solution, and melamine was dissolved in 30mL of deionized water to prepare an aqueous melamine solution. Adding chloroplatinic acid hexahydrate into the glucose aqueous solution, reacting for 0.5h, then adding a melamine aqueous solution, and continuing to react for 0.5 h. Then, conductive carbon black is added into the solution and is subjected to ultrasonic treatment for 100W for 1 h. Then freeze-dried to completely remove the deionized water. Finally, the sample was placed in a tube furnace at a flow rate of 100mL/min N 2 Heating to 500 ℃ at the speed of 2 ℃/min under the atmosphere, and keeping for 5h to obtain the pre-catalyst. The prepared pre-catalyst is combined with a working electrode and then connected by using a three-electrode system. O was passed through an electrolyte (phosphate buffer solution at pH 7.4, 30mM) at a rate of 100ml/min 2 For 30min, adding O in the electrolyte 2 Saturation (electrocatalytic oxidation of hydrogen peroxide to O 2 Therefore, with O 2 As the treatment atmosphere for the present precatalyst). Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 50ml/min, the scanning speed is 50mV/s, the scanning times are 100 times, and the scanning range is-2V. After completion, Pt NCs1-D was obtained.
TEM characterization showed that the particle size of the Pt nanoclusters supported on conductive carbon black was 6.1nm, and Inductively Coupled Plasma (ICP) analysis results showed that the Pt content in this sample was 0.91 wt%.
Comparative example 5: preparation of Pt nanocluster catalyst Pt NCs1-E
1g of conductive carbon black material, 26.5mg of chloroplatinic acid hexahydrate, 55.4mg of glucose and 43.1mg of melamine were weighed (the molar ratio of chloroplatinic acid hexahydrate, glucose and melamine calculated as the molar amount of the nitrogen atom was 1:6: 40). Glucose was dissolved in 30mL of deionized water to prepare an aqueous glucose solution, and melamine was dissolved in 30mL of deionized water to prepare an aqueous melamine solution. Adding chloroplatinic acid hexahydrate into the glucose aqueous solution, reacting for 0.5h, then adding a melamine aqueous solution, and continuing to react for 0.5 h. Then, conductive carbon black is added into the solution and is subjected to ultrasonic treatment for 100W for 1 h. Then freeze-dried to completely remove the deionized water. Finally, the sample was placed in a tube furnace at a flow rate of 100mL/min N 2 Heating to 500 ℃ at the speed of 2 ℃/min under the atmosphere, and keeping for 5h to obtain the pre-catalyst. The prepared pre-catalyst is combined with a working electrode and then connected by using a three-electrode system. O was passed through an electrolyte (phosphate buffer solution at pH 7.4, 30mM) at a rate of 100ml/min 2 For 30min, adding O in the electrolyte 2 Saturation (electrocatalytic oxidation of hydrogen peroxide to O 2 Therefore, with O 2 As the treatment atmosphere for the present precatalyst). Then, the cyclic voltammetry treatment of the electrode is carried out under the condition of continuously ventilating at the speed of 50ml/min, the scanning speed is 50mV/s, the scanning times are 100 times, and the scanning range is-2V. After completion, Pt NCs1-E was obtained.
TEM characterization showed that the particle size of the Pt nanoclusters supported on conductive carbon black was 5.3nm, and Inductively Coupled Plasma (ICP) analysis results showed that the Pt content in this sample was 0.81 wt%.
Comparative example 6: preparation of Pt nanocluster catalyst Pt NCs2-F
1g of conductive carbon black material and 26.5mg of chloroplatinic acid hexahydrate (H) were weighed 2 PtCl 6 ·6H 2 O), 9.3mg of glucose and 10.77mg of melamine (chloroplatinic acid hexa calculated as molar mass of platinum atoms)The molar ratio of hydrate, glucose and melamine, calculated as the molar amount of nitrogen atoms, was 1:1: 10). Glucose was dissolved in 30mL of deionized water to prepare an aqueous glucose solution, and melamine was dissolved in 30mL of deionized water to prepare an aqueous melamine solution. Adding chloroplatinic acid hexahydrate into the glucose aqueous solution, reacting for 0.5h, then adding a melamine aqueous solution, and continuing to react for 0.5 h. Then, conductive carbon black is added into the solution and is subjected to ultrasonic treatment for 100W for 1 h. Then freeze-dried to completely remove the deionized water. Finally, the sample was placed in a tube furnace at a flow rate of 100mL/min N 2 Heating to 500 ℃ at the speed of 2 ℃/min under the atmosphere and keeping for 5h to obtain the Pt NCs 2-F.
TEM characterization showed that the particle size of the Pt nanoclusters supported on conductive carbon black was 1.6nm, and Inductively Coupled Plasma (ICP) analysis results showed that the Pt content in this sample was 3.99 wt%.
Comparative example 7: construction of Hydrogen peroxide biosensor
Hydrogen peroxide sensors were prepared by modifying the working electrodes with the metal cluster catalysts prepared in comparative examples 1 to 6, respectively, according to the method of example 5, and the hydrogen peroxide detection performance thereof is shown in table 3 below.
TABLE 3
Figure BDA0003570054760000231
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (12)

1. A method for preparing a carbon-supported metal nanocluster catalyst, comprising:
preparing a metal salt solution, wherein the metal salt solution comprises a metal salt, a metal chelate, a nitrogen source and a solvent;
mixing the metal salt solution with a carbon material and freeze-drying to obtain a freeze-dried sample;
roasting the freeze-dried sample in an inert atmosphere to obtain a carbon-supported metal nanocluster pre-catalyst; and
and combining the metal nanocluster precatalyst with a working electrode, putting the combined metal nanocluster precatalyst into electrolyte containing a guiding agent, and carrying out electrochemical oxidation reduction treatment on the metal nanocluster precatalyst through cyclic voltammetry to obtain the stable metal nanocluster catalyst, wherein the guiding agent is a target product of a reaction which can be catalyzed by the metal nanocluster catalyst.
2. The method according to claim 1, wherein the molar ratio of the metal salt, the metal chelate compound and the nitrogen source calculated as the molar amount of metal atoms is 1 (1-5) to (5-30).
3. The production method according to claim 1 or 2,
the metal salt is one or more of Pt salt, Au salt, Ag salt, Ir salt, Pd salt and Rh salt;
the metal chelate is a saccharide;
the nitrogen source is one or more of melamine, dicyandiamide and urea;
the solvent is water or a mixture of water and alcohols;
the carbon material is one or more of carbon nanoparticles, conductive carbon black, lamp black carbon, carbon fibers, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene fibers, two-dimensional graphene paper, three-dimensional carbon foam and three-dimensional graphene aerogel; preferably, the carbon material is one or more of single-walled carbon nanotubes and multi-walled carbon nanotubes; preferably, the carbon material is modified with N atoms or S atoms.
4. Preparation according to claim 1 or 2The method is characterized in that the guiding agent is O 2 、H 2 、CO、CH 4 、H 2 O 2 Sodium nitrite, formic acid or acetic acid.
5. The method according to claim 1,
the scanning speed of the electrochemical oxidation-reduction treatment is 10-200 mV/s; the scanning potential window is-5V, and the scanning times are 1-500.
6. The carbon-supported metal nanocluster catalyst obtained by the production method as recited in any one of claims 1 to 5, wherein the metal nanoclusters have a particle size of 0.5 to 2 nm; the content of the metal element is 0.5 to 15% by weight based on the total mass of the metal nanocluster catalyst.
7. A biosensor, which comprises the carbon-supported metal nanocluster catalyst according to claim 6.
8. The biosensor of claim 7, comprising:
a base layer;
the working electrode is arranged on the surface of the substrate layer; and
an electrocatalytic layer disposed on a surface of the working electrode and including the carbon-supported metal nanocluster catalyst.
9. The biosensor of claim 8, further comprising:
the biological catalysis layer is arranged on the surface of the electrocatalytic layer and comprises biological enzymes; preferably, the biological enzyme is glucose oxidase, galactose oxidase, cholesterol oxidase, amino acid oxidase, alcohol oxidase, lactate oxidase, or uricase.
10. The biosensor of claim 9, further comprising:
the macromolecule layer is arranged on the surface of the biological catalytic layer.
11. Use of the biosensor of claim 7 or 8 for detecting H 2 O 2 The use of the concentration.
12. Use of the biosensor of claim 9 or 10 for detecting the concentration of biomolecules, such as blood glucose, galactose, cholesterol, amino acids, alcohols, lactic acid or uric acid.
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Citations (4)

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CN111408366A (en) * 2020-03-03 2020-07-14 合肥枡水新能源科技有限公司 Preparation method of carbon-supported metal nanocluster catalyst
CN111682223A (en) * 2020-06-12 2020-09-18 山东理工大学 Preparation of in-situ synthesized nitrogen-doped carbon sheet supported (Co, Ni, Fe) nanoparticle electrocatalyst
CN112513284A (en) * 2018-04-18 2021-03-16 美题隆公司 Electrode for biosensor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101451254A (en) * 2008-12-04 2009-06-10 合肥工业大学 One-step electrochemistry reduction method for preparing nano scale metal simple substance cobalt
CN112513284A (en) * 2018-04-18 2021-03-16 美题隆公司 Electrode for biosensor
CN111408366A (en) * 2020-03-03 2020-07-14 合肥枡水新能源科技有限公司 Preparation method of carbon-supported metal nanocluster catalyst
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