CN112899820A - Cu-Ni-Co-O solid solution nano fiber material and preparation method and application thereof - Google Patents
Cu-Ni-Co-O solid solution nano fiber material and preparation method and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
Abstract
The invention relates to the technical field of electrocatalysis and electrochemical glucose sensing, in particular to a Cu-Ni-Co-O solid solution nanofiber material and a preparation method and application thereof. The electrospun Cu-Ni-Co-O solid solution nanofiber electrode material has higher sensitivity when being used for detecting electrochemical glucose, and is simple to prepare. The multi-chemical valence states of Cu, Ni and Co elements in the Cu-Ni-Co-O solid solution nanofiber material and the unique nano-structure characteristic of the electrospun nanofiber can synergistically improve the electrocatalytic performance and increase the sensitivity of a glucose sensor.
Description
Technical Field
The invention relates to the technical field of electrocatalysis and electrochemical glucose sensing, in particular to a Cu-Ni-Co-O solid solution nanofiber material and a preparation method and application thereof.
Background
With the increasing living standard of people, the occurrence of diabetes, namely 'rich disease' is more frequent. A blood glucose meter (glucose biosensor) provides convenience for a diabetic to detect the blood glucose concentration. Among the many types of glucose sensors, electrochemical glucose sensors are distinguished by their high sensitivity and selectivity, rapid response, and low detection limit. Among them, in the field of electrochemical glucose sensing, the conventional glucose sensor using a bio-enzyme method has excellent selectivity due to the use of glucose oxidase or glucose dehydrogenase. However, enzyme-based sensors involve complicated multi-step immobilization procedures, are costly, and suffer from thermal and chemical instability that is difficult to solve. Therefore, the design of a non-enzymatic glucose sensor with high sensitivity and good stability has attracted great interest to researchers.
At present, metal oxides (especially transition metal oxides) are widely used in the design of non-enzymatic glucose sensors. Different metal oxides have different crystal structures, electronic conductivities and electrocatalytic properties, resulting in large differences in the performance of sensors constructed from their designs. Among the transition metal oxides known for use in non-enzymatic glucose sensors, NiCo2O4The electrocatalytic activity of the composite material is excellent, has high sensitivity and stability, and is an excellent electrode material for the electrocatalytic oxidation of glucose. To further improve NiCo2O4In the above-mentioned electrocatalytic properties, researchers have attempted to improve the properties by various methods. Such as: (1) in 2016, Youngkwan Lee et al reported direct growth of multilayer NiCo on stainless steel surfaces by sacrificial template method2O4Hollow nanorods and their use in electrochemical glucose sensing [ Yang J, Cho M, Lee Y. Synthesis of theoretical NiCo2O4 hollow nanorods via sacrificial-template accelerate hydrolysis for electrochemical glucose oxidation[J].Biosensors andBioelectronics 75(2016)15-22](ii) a (2) In 2016, Leilei Zhang et al reported a NiCo with a core-shell structure2O4@ polyaniline (NiCo)2O4@ PANI) nanocomposite and its use in electrochemical glucose detection [ Zhiyuan, Yu, Hejun, et al2O4@Polyaniline core–shell nanocomposite for sensitive determination of glucose[J].Biosensors and Bioelectronics 75(2016)161-165](ii) a (3) In 2018, Qiaohui Guo et al reported a NiCo-based assay2O4Nano-needle modified electrospun carbon nano-composite fiber membrane and its use in electrochemical glucose detection [ Liu L, Wang Z, Yang J, et al2O4 nanoneedle-decorated electrospun carbon nanofiber nanohybrids for sensitive non-enzymatic glucose sensors[J].Sensors and Actuators B 258(2018)920-928]. However, the materials obtained by the methods (1) and (2) above have low sensitivity to glucose; NiCo obtained by the method of (3)2O4The sensitivity of the nanoneedle array to glucose is improved, but the preparation conditions are harsh, and high-temperature calcination at 900 ℃ needs to be carried out under the protection of inert atmosphere, so that the cost is higher.
Disclosure of Invention
The invention aims to provide an electrospun Cu-Ni-Co-O solid solution nanofiber electrode material and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a Cu-Ni-Co-O solid solution nano fiber material which has a three-dimensional porous net felt structure, and Cu ions are embedded into NiCo2O4Form a Cu-Ni-Co-O solid solution in the crystal lattice; the Cu-Ni-Co-O solid solution nanofiber material is characterized in that the molar ratio of Cu to Ni to Co to O in the Cu-Ni-Co-O solid solution nanofiber material is x (1-x) to 2:4, wherein x is 0.05-0.25; the Cu-Ni-Co-O solid solution nanofiber material is nanoscale in diameter and micron in length.
Preferably, the diameter of the Cu-Ni-Co-O solid solution nanofiber material is 100-300 nm.
The invention provides a preparation method of the Cu-Ni-Co-O solid solution nanofiber material, which is characterized by comprising the following steps of:
dissolving copper salt, nickel salt, cobalt salt and a template agent in a solvent to obtain spinning solution; the molar ratio of the copper in the copper salt to the nickel in the nickel salt to the cobalt in the cobalt salt is x (1-x) 2, wherein x is 0.05-0.25;
performing electrostatic spinning on the spinning solution to obtain metal salt/template agent composite nanofibers;
and calcining the metal salt/template agent composite nanofiber in an air atmosphere to obtain the Cu-Ni-Co-O solid solution nanofiber material.
Preferably, the template agent comprises polyvinylpyrrolidone, polyacrylonitrile or polyvinyl alcohol; the solvent comprises N, N-dimethylformamide, ethanol, chloroform or water; the ratio of the total mass of the copper salt, the nickel salt and the cobalt salt to the dosage of the solvent is (0.3-0.6) g (8-12) mL; the dosage ratio of the template agent to the solvent is (1.2-1.6) g:10 mL.
Preferably, the electrospinning conditions include: the spinning voltage is 7-20 kV, the receiving distance is 10-15 cm, and the diameter of the nozzle is 0.4-0.8 mm.
Preferably, the calcining temperature is 400-600 ℃, and the heat preservation time is 0.5-2 h.
The invention provides an application of the Cu-Ni-Co-O solid solution nanofiber material prepared by the scheme or the Cu-Ni-Co-O solid solution nanofiber material prepared by the preparation method in non-enzymatic electrochemical detection of glucose.
Preferably, the application mode is as follows: preparing the Cu-Ni-Co-O solid solution nanofiber material into a working electrode for detecting glucose;
the preparation method of the working electrode comprises the following steps:
dispersing the Cu-Ni-Co-O solid solution nano fiber material into a binder to obtain a Cu-Ni-Co-O solid solution nano fiber/binder suspension;
and coating the Cu-Ni-Co-O solid solution nanofiber/binder turbid liquid on the surface of a conductive current collector, calcining the conductive current collector coated with the turbid liquid, and removing the binder to obtain the working electrode.
Preferably, the binder comprises triton, Nafion solution, conductive polymer PEDOT or PTFE; the dosage ratio of the Cu-Ni-Co-O solid solution nano-fiber material to the binder is (10-30) mg:0.1 mL.
Preferably, the conductive current collector comprises ITO conductive glass, FTO conductive glass, stainless steel mesh, carbon cloth, copper foam or nickel foam; the calcining temperature is 350-450 ℃.
The invention provides a Cu-Ni-Co-O solid solution nano fiber material which has a three-dimensional porous net felt structure, and Cu ions are embedded into NiCo2O4Form a Cu-Ni-Co-O solid solution in the crystal lattice. On one hand, the Cu-Ni-Co-O solid solution has a three-dimensional porous net felt structure, can adsorb more glucose molecules, and meanwhile, the overlong one-dimensional nanofiber structure can shorten an ion transmission path, so that electrons can be conveniently and rapidly transferred, and the sensitivity of a glucose sensor is improved; on the other hand, the Cu-Ni-Co-O solid solution has a large amount of metal ions (Cu)2+、Ni2+、Co3+) And more variable price conversion The glucose sensor is easy to generate oxidation-reduction reaction with glucose in an electrochemical environment, and further improves the sensitivity of glucose detection.
Compared with copper ion interstitial doped NiCo2O4The doping amount of copper ions is limited (within 10 percent), and the invention embeds the copper ions into NiCo2O4The content of copper is improved in the crystal lattice, so that the sensitivity of the sensor is improved; in addition, as the ionic radii of the Cu and Ni elements are relatively close, the formed Cu-Ni-Co-O solid solution has almost no lattice mismatch, so that the Cu-Ni-Co-O solid solution nanofiber material has higher stability.
The invention also provides a preparation method of the Cu-Ni-Co-O solid solution nanofiber material, and the preparation method is simple by simply calcining the spinning solution after electrostatic spinning.
Drawings
FIG. 1 shows Cu prepared in example 1 of the present invention0.05Ni0.95Co2O4Scanning electron microscope photographs of the solid solution nanofiber material;
FIG. 2 shows Cu prepared in example 2 of the present invention0.15Ni0.85Co2O4Scanning electron microscope photographs of the solid solution nanofiber material;
FIG. 3 shows Cu prepared in example 3 of the present invention0.25Ni0.75Co2O4Scanning electron microscope photographs of the solid solution nanofiber material;
FIG. 4 is a schematic representation of NiCo prepared according to comparative example 1 of the present invention2O4Scanning electron micrographs of the nanofiber material;
FIG. 5 is a graph of CuCo prepared in comparative example 2 of the present invention2O4Scanning electron microscope photos of the nanofiber material;
FIG. 6 is a 10% Cu-NiCo alloy prepared according to comparative example 3 of the present invention2O4Scanning electron microscope photos of the nanofiber material;
FIG. 7 is an X-ray diffraction pattern of the nanofiber materials prepared in examples 1 to 3 of the present invention and comparative examples 1 to 3, wherein: a is Cu0.05Ni0.95Co2O4A solid solution nanofiber material, B is Cu0.15Ni0.85Co2O4A solid solution nanofiber material, C being Cu0.25Ni0.75Co2O4A solid solution nanofiber material, D is NiCo2O4Nanofibers, E is CuCo2O4Nanofibers, F is 10% Cu-NiCo2O4A nanofiber;
FIG. 8 is a Cu film prepared in comparative example 4 of the present invention0.35Ni0.65Co2O4An X-ray diffraction pattern of the nanofiber material;
FIG. 9 shows Cu prepared in example 3 of the present invention0.25Ni0.75Co2O4High resolution transmission electron microscope photographs of the solid solution nanofiber material;
FIG. 10 shows Cu prepared in example 3 of the present invention0.25Ni0.75Co2O4And (3) an amperometric current response graph of the solid solution nanofiber electrode material during glucose sensing performance test.
Detailed Description
The invention provides a Cu-Ni-Co-O solid solution nano fiber material which has a three-dimensional porous net felt structure, and Cu ions are embedded into NiCo2O4Form a Cu-Ni-Co-O solid solution in the crystal lattice.
In the invention, the molar ratio of Cu, Ni, Co and O in the Cu-Ni-Co-O solid solution nano-fiber material is x (1-x) to 2:4, wherein x is 0.05-0.25, preferably 0.25. The invention embeds copper ions into NiCo2O4The content of copper is improved in the crystal lattice, so that the sensitivity of the sensor is improved; in addition, as the ionic radii of Cu and Ni elements are relatively similar, the formed Cu-Ni-Co-O solid solution has almost no lattice mismatch, so that the Cu-Ni-Co-O solid solution nanofiber material has higher stability.
In the invention, the diameter of the Cu-Ni-Co-O solid solution nanofiber material is nano-scale, and is preferably 100-300 nm; the length is in the order of micrometers, i.e. > 1 μm. The overlong one-dimensional nanofiber structure of the Cu-Ni-Co-O solid solution nanofiber material can shorten an ion transmission path, facilitate rapid electron transfer and further improve the sensitivity of a glucose sensor.
The Cu-Ni-Co-O solid solution is a three-dimensional porous net felt nanofiber, and has the advantages of high specific surface area, large porosity, large length-diameter ratio and the like, more glucose molecules can be adsorbed by the high specific surface area and the large porosity, the large length-diameter ratio can shorten an ion transmission channel, electrons can be conveniently and rapidly transferred, and the sensitivity of a glucose sensor is further improved.
In addition, the Cu-Ni-Co-O solid solution of the present invention has more metal ions (Cu)2+、Ni2+、Co3+) And more variable price conversionThe glucose sensor is easy to generate oxidation-reduction reaction with glucose in an electrochemical environment, and further improves the sensitivity of glucose detection.
The invention provides a preparation method of the Cu-Ni-Co-O solid solution nanofiber material in the scheme, which comprises the following steps:
dissolving copper salt, nickel salt, cobalt salt and a template agent in a solvent to obtain spinning solution;
performing electrostatic spinning on the spinning solution to obtain metal salt/template agent composite nanofibers;
and calcining the metal salt/template agent composite nanofiber in an air atmosphere to obtain the Cu-Ni-Co-O solid solution nanofiber material.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
According to the invention, copper salt, nickel salt, cobalt salt and a template agent are dissolved in a solvent to obtain a spinning solution.
In the present invention, the copper salt preferably includes copper acetate monohydrate, copper nitrate, copper sulfate, copper chloride or the like, more preferably copper acetate monohydrate; the nickel salt preferably comprises nickel acetate tetrahydrate, nickel nitrate, nickel sulfate or nickel chloride and the like, and more preferably nickel acetate tetrahydrate; the cobalt salt preferably includes cobalt acetate tetrahydrate, cobalt nitrate, cobalt sulfate, cobalt chloride or the like, and more preferably cobalt acetate tetrahydrate.
In the present invention, the templating agent preferably includes polyvinylpyrrolidone, polyacrylonitrile, or polyvinyl alcohol, more preferably polyvinylpyrrolidone; in the present invention, the molecular weight of the polyvinylpyrrolidone is preferably 90 ten thousand or more; the molecular weight of the polyacrylonitrile is preferably more than 150 ten thousand; the molecular weight of the polyvinyl alcohol is preferably 8 ten thousand or more.
In the present invention, the solvent preferably includes N, N-dimethylformamide, ethanol, chloroform or water, and more preferably N, N-dimethylformamide. According to the present invention, it is preferable to select a suitable solvent capable of completely dissolving the copper salt, the nickel salt, the cobalt salt and the templating agent, depending on the kind of the templating agent. In the present invention, when the templating agent is polyvinylpyrrolidone, the solvent is preferably N, N-dimethylformamide.
In the present invention, the process of dissolution is preferably: adding copper salt, nickel salt and cobalt salt into a solvent, fully stirring and dissolving, then adding a template agent, and obtaining the spinning solution after dissolving.
In the invention, the molar ratio of copper in the copper salt, nickel in the nickel salt and cobalt in the cobalt salt is preferably x (1-x):2, wherein x is 0.05-0.25, and is preferably 0.25.
In the invention, the ratio of the total mass of the copper salt, the nickel salt and the cobalt salt to the amount of the solvent is preferably (0.3-0.6) g, (8-12) mL, and more preferably (0.3-0.6) g, 10 mL.
In the present invention, the amount ratio of the template to the solvent is preferably (1.2 to 1.6) g to 10mL, and more preferably (1.3 to 1.5) g to 10 mL.
According to the invention, the dosage of the copper salt, the nickel salt, the cobalt salt, the template agent and the solvent is controlled within the range, so that the spinning solution with proper viscosity can be obtained, and further the subsequent spinning can be smoothly carried out.
After the spinning solution is obtained, the spinning solution is subjected to electrostatic spinning to obtain the metal salt/template agent composite nanofiber.
The invention has no special requirements on the specific implementation mode of the electrostatic spinning, and the electrostatic spinning mode well known in the field can be adopted. In the embodiment of the invention, the spinning solution is filled into a medical injector with a nozzle, the distance between the nozzle and a grounded receiving plate is adjusted, and a gold electrode is put into the spinning solution to apply high spinning pressure to carry out electrostatic spinning.
In the present invention, the conditions of the electrospinning preferably include: the spinning voltage is 7-20 kV, the receiving distance is 10-15 cm, and the diameter of a nozzle is 0.4-0.8 mm; further, the spinning voltage is preferably 7-15 kV, the receiving distance is preferably 12-15 cm, and the diameter of the nozzle is preferably 0.4-0.6 mm.
After electrostatic spinning, the metal salt/template agent composite nanofiber is obtained, wherein the metal salt comprises copper salt, nickel salt and cobalt salt.
After the metal salt/template agent composite nanofiber is obtained, the metal salt/template agent composite nanofiber is calcined in the air atmosphere to obtain the Cu-Ni-Co-O solid solution nanofiber material.
In the invention, the calcination temperature is preferably 400-600 ℃, more preferably 450-550 ℃, and most preferably 500 ℃; the calcination heat preservation time is preferably 0.5-2 h, and more preferably 1-2 h.
According to the invention, the temperature is preferably raised from room temperature to the calcining temperature, and the heating rate is preferably 1-5 ℃/min, and more preferably 2 ℃/min. The invention controls the heating rate in the range, which can prevent the collapse of the template agent and the incapability of forming the nano fiber caused by the excessively high heating rate and can also prevent the overlarge crystal grains forming the nano fiber caused by the excessively low heating rate.
In the calcining process, the template agent is removed to form a three-dimensional porous net felt nanofiber structure and a Cu-Ni-Co-O solid solution.
The invention provides an application of the Cu-Ni-Co-O solid solution nanofiber material prepared by the scheme or the Cu-Ni-Co-O solid solution nanofiber material prepared by the preparation method in non-enzymatic electrochemical detection of glucose.
The invention further preferably prepares the Cu-Ni-Co-O solid solution nano-fiber material into a working electrode for detecting glucose.
In the present invention, the method for preparing the working electrode preferably includes the steps of:
dispersing the Cu-Ni-Co-O solid solution nano fiber material into a binder to obtain a Cu-Ni-Co-O solid solution nano fiber/binder suspension;
and coating the Cu-Ni-Co-O solid solution nanofiber/binder turbid liquid on the surface of a conductive current collector, calcining the conductive current collector coated with the turbid liquid, and removing the binder to obtain the working electrode.
The invention has no special requirement on the specific type of the binder, and the specific binder can be, but is not limited to, triton, Nafion solution, conductive polymer PEDOT and PTFE. In the invention, the dosage ratio of the Cu-Ni-Co-O solid solution nano-fiber material to the binder is preferably (10-30) mg:0.1mL, and more preferably 20mg:0.1 mL. According to the invention, the Cu-Ni-Co-O solid solution nano fiber material is preferably added into a binder for ultrasonic treatment to obtain a Cu-Ni-Co-O solid solution nano fiber/binder suspension.
The invention has no special requirement on the specific type of the conductive current collector, and the conductive current collector well known in the art can be adopted, and the specific type of the conductive current collector can be, but is not limited to, ITO conductive glass, FTO conductive glass, stainless steel mesh, carbon cloth, copper foam and nickel foam.
In the present invention, each 0.25cm2The using amount of the Cu-Ni-Co-O solid solution nanofiber/binder suspension on the conductive current collector is preferably 20-40 mu L, and more preferably 30 mu L. In the embodiment of the invention, the conductive current collector is ITO conductive glass; the size of the ITO conductive glass is 1cm multiplied by 2cm, and the effective coating size is 0.5cm multiplied by 0.5 cm.
In the invention, the calcining temperature is preferably 350-450 ℃, and more preferably 400 ℃; the holding time of the calcination is preferably 2 hours; the calcination is preferably carried out in an air atmosphere. After calcination, the binder is removed and the electrode material (i.e., the Cu-Ni-Co-O solid solution nanofiber material) and the conductive current collector can be well adhered together, so that the electrode material is prevented from falling off when tested in an electrolyte.
The invention has no special requirements on the detection process of the glucose, and the working electrode is directly used for detecting the glucose, which is common knowledge in the field and is not described again.
The Cu-Ni-Co-O solid solution nano-fiber material provided by the invention and the preparation method and application thereof are explained in detail below with reference to examples, but the Cu-Ni-Co-O solid solution nano-fiber material is not to be construed as limiting the protection scope of the invention.
Example 1
0.025mmol of copper acetate monohydrate, 0.475mmol of nickel acetate tetrahydrate and 1mmol of cobalt acetate tetrahydrate were added to 10ml of N, N-dimethylformamide and sufficiently stirred to dissolve them, and then 1.5g of high molecular weight polyvinylpyrrolidone was dissolved in the above solution and sufficiently stirred to dissolve it to obtain a spinning solution. Then, the spinning solution was put into a medical syringe having a nozzle with a diameter of 0.4mm, the distance between the nozzle and the grounded receiving plate was kept at 15cm, and a gold electrode was put into the solution and subjected to electrostatic spinning at a high voltage of 7kV to prepare a metal salt/templating agent composite nanofiber. Finally, the metal salt/template composite is calcined in a muffle furnace at a high temperature of 500 ℃ at a rate of 2 ℃/minNanofibers for 2 hours to obtain Cu0.05Ni0.95Co2O4A solid solution nanofiber material.
Produced Cu0.05Ni0.95Co2O4Scanning electron micrograph of solid solution nanofiber is shown in FIG. 1, from which the Cu produced is clearly visible0.05Ni0.95Co2O4The solid solution nanofiber is a three-dimensional porous net felt structure with the diameter of about 100-300 nm.
The obtained Cu0.05Ni0.95Co2O4The solid solution nanofiber is subjected to X-ray diffraction pattern analysis, and the result is shown as a curve A in figure 7, wherein the X-ray diffraction pattern and NiCo are shown2O4The characteristic diffraction peaks are completely consistent, and the characteristic diffraction peak related to Cu is not observed, which shows that the spinel structure of the prepared nanofiber material is not changed, and proves that the Cu is successfully prepared0.05Ni0.95Co2O4A solid solution material.
20mg of Cu obtained in this example0.05Ni0.95Co2O4Adding the solid solution nano-fiber material into 0.1mL of triton, and carrying out ultrasonic treatment for 1min to obtain Cu0.05Ni0.95Co2O4Solid solution nanofiber/triton suspension. Taking 30 mu L of Cu0.05Ni0.95Co2O4And (3) coating the solid solution nanofiber/triton suspension on the surface of 1cm multiplied by 2cm of ITO conductive glass, wherein the effective coating area is 0.5cm multiplied by 0.5cm, then heating to 400 ℃ at the speed of 5 ℃/min in a muffle furnace, calcining the ITO conductive glass coated with the suspension for 2 hours, and removing the triton to obtain the working electrode.
The working electrode in the embodiment is connected with a mercury/mercury oxide reference electrode and a platinum mesh counter electrode to establish a three-electrode system, and the three-electrode system is connected with an electrochemical workstation to detect the concentration of glucose in the solution to be detected. Measuring glucose concentration by amperometric amperometry (I-T) at 0.55V, adding 20mL of 0.1mol/L sodium hydroxide solution as electrolyte into beaker, and adding different amounts of glucose at certain intervalsGlucose, and the specific steps of adding are as follows: the interval time of dripping glucose every time is 50 s; first, 10. mu.L of a 0.1M glucose solution (glucose concentration in the solution increased by 0.05mM after each addition) and 20. mu.L of a 0.1M glucose solution (glucose concentration in the solution increased by 0.1mM after addition) were added twice; four more 4. mu.L 1M glucose solutions were added (glucose concentration in the solution increased by 0.2mM after each addition, at which time the glucose concentration in the solution was 1 mM); then, 5. mu.L of 1M glucose solution was added four times (glucose concentration in the solution increased by 0.25mM after each addition), and finally, 10. mu.L of 1M glucose solution was added eight times (glucose concentration in the solution increased by 0.5mM after each addition, and glucose concentration in the final solution was 6 mM). And detecting current response values of glucose with different concentrations, and calculating the sensitivity: the sensitivity is 1446 muA.mM at a glucose concentration of 0-2 mM-1·cm-2(ii) a The sensitivity is 428.4 muA.mM when the glucose concentration is 2-6 mM-1·cm-2。
Example 2
The difference from example 1 is that copper acetate monohydrate and nickel acetate tetrahydrate were added in amounts of 0.075mmol and 0.425mmol, respectively, corresponding to a molar ratio of copper, nickel and cobalt of 0.15:0.85:2 to produce Cu0.15Ni0.85Co2O4A solid solution nanofiber material.
Produced Cu0.15Ni0.85Co2O4Scanning electron micrograph of solid solution nanofibers is shown in FIG. 2, from which the Cu produced is clearly visible0.15Ni0.85Co2O4The solid solution nanofiber is a three-dimensional porous net felt structure with the diameter of about 100-200 nm.
The obtained Cu0.15Ni0.85Co2O4The solid solution nano-fiber is subjected to X-ray diffraction pattern analysis, and the result is shown as a curve B in figure 7, wherein the X-ray diffraction pattern and NiCo thereof2O4The characteristic diffraction peaks are completely consistent, and the characteristic diffraction peak related to Cu is not observed, which shows that the spinel structure of the prepared nano-fiber material is not changed, and proves that the nano-fiber material is successfully preparedCu0.15Ni0.85Co2O4A solid solution material.
Example 3
The difference from example 1 is that copper acetate monohydrate and nickel acetate tetrahydrate were added in amounts of 0.125mmol and 0.375mmol, respectively, corresponding to a molar ratio of copper, nickel and cobalt of 0.25:0.75:2 to produce Cu0.25Ni0.75Co2O4A solid solution nanofiber material.
Produced Cu0.25Ni0.75Co2O4Scanning electron micrograph of solid solution nanofibers is shown in FIG. 3, from which the Cu produced is clearly visible0.25Ni0.75Co2O4The solid solution nanofiber is a three-dimensional porous net felt structure with the diameter of about 100-200 nm.
The obtained Cu0.25Ni0.75Co2O4The solid solution nanofiber is subjected to X-ray diffraction pattern analysis, and the result is shown as a curve C in figure 7, wherein the X-ray diffraction pattern and NiCo are shown in2O4The characteristic diffraction peaks are completely consistent, and the characteristic diffraction peak related to Cu is not observed, which shows that the spinel structure of the prepared nanofiber material is not changed, and proves that the Cu is successfully prepared0.25Ni0.75Co2O4A solid solution material.
FIG. 9 shows Cu prepared in this example0.25Ni0.75Co2O4High resolution TEM image of solid solution nanofiber material, from which a lattice spacing of 0.204nm, corresponding to NiCo, can be clearly observed2O4The (400) crystal face of the crystal is consistent with the X-ray diffraction pattern result.
Cu obtained in this example was treated by the method of example 10.25Ni0.75Co2O4The solid solution nanofiber material was prepared into a working electrode, glucose concentration was measured by amperometric amperometry (I-T) in the same manner as in example 1, and the results are shown in fig. 10, and the sensitivity thereof was calculated as follows: the sensitivity is 2889.6 muA.mM when the glucose concentration is 0-2 mM-1·cm-2(ii) a The sensitivity is 1021.6 muA.mM when the glucose concentration is 2-6 mM-1·cm-2。
Comparative example 1
The difference from example 1 is that copper acetate monohydrate was not added, the amount of nickel acetate tetrahydrate added was 0.5mmol, corresponding to a molar ratio of nickel to cobalt of 1:2, and NiCo was obtained2O4And (3) nano fibers.
The NiCo is prepared2O4The scanning electron micrograph of the nanofibers is shown in FIG. 4, from which it is clear that NiCo was produced2O4The nanofiber is of a three-dimensional porous net felt structure with the diameter of about 100-300 nm.
The NiCo prepared is2O4The nanofiber is subjected to X-ray diffraction pattern analysis, and the result is shown as a D curve in figure 7, wherein the X-ray diffraction pattern and NiCo are2O4The characteristic diffraction peaks are completely consistent, and the successful preparation of NiCo with a spinel structure is proved2O4A material.
Comparative example 2
The difference from example 1 is that nickel acetate tetrahydrate was not added, the amount of copper acetate monohydrate added was 0.5mmol, and the corresponding molar ratio of copper to cobalt was 1:2, to obtain CuCo2O4And (3) nano fibers.
The obtained CuCo2O4The scanning electron micrograph of the nanofibers is shown in FIG. 5, from which the CuCo produced is clearly seen2O4The nanofiber is of a three-dimensional porous net felt structure with the diameter of about 100-300 nm.
The prepared CuCo2O4The nano-fiber is subjected to X-ray diffraction pattern analysis, and the result is shown as E curve in figure 7, and the X-ray diffraction pattern and CuCo thereof2O4The characteristic diffraction peaks are completely consistent, and the successful preparation of the CuCo with the spinel structure is proved2O4A material.
Comparative example 3
The difference from example 1 is that the amounts of copper acetate monohydrate and nickel acetate tetrahydrate were 0.05mmol and 0.5mmol, respectively, corresponding to the moles of copper, nickel and cobaltThe ratio is 0.1:1:2, and 10 percent of copper interstitial doped NiCo is prepared2O4Nanofibers, 10% Cu-NiCo2O4And (3) nano fibers.
The 10% Cu-NiCo is obtained2O4Scanning electron micrograph of the nanofibers is shown in FIG. 6, from which it is clear that 10% Cu-NiCo was produced2O4The nanofiber is of a three-dimensional porous net felt structure with the diameter of about 100-300 nm.
The prepared 10% Cu-NiCo2O4The nanofiber is subjected to X-ray diffraction pattern analysis, and the result is shown as a curve F in FIG. 7, wherein the X-ray diffraction pattern and NiCo are2O4The characteristic diffraction peaks of (a) are substantially uniform.
Comparative example 4
The difference from example 1 is that copper acetate monohydrate and nickel acetate tetrahydrate were added in amounts of 0.175mmol and 0.325mmol, respectively, corresponding to a molar ratio of copper, nickel and cobalt of 0.35:0.65:2 to produce Cu0.35Ni0.65Co2O4A nanofiber material.
The obtained Cu0.35Ni0.65Co2O4The nanofiber is subjected to X-ray diffraction pattern analysis, the result is shown in figure 8, and the X-ray diffraction pattern of the nanofiber is divided by NiCo2O4In addition to the characteristic diffraction peak of CuO, the characteristic diffraction peak of CuO is observed, which indicates that the prepared nano-fiber material is no longer a pure-phase Cu-Ni-Co-O solid solution.
The nanofibers of examples 2-3 and comparative examples 1-4 were used to detect glucose in the same manner as in example 1, and the calculated sensitivities are shown in Table 1.
TABLE 1 sensitivity (unit: μ A. multidot. mM) of examples 1 to 3 and comparative examples 1 to 4-1·cm-2)
As is clear from the results of Table 1, the present invention is achieved by introducing Cu into NiCo2O4And can be formed by controlling the doping amount of CuThe Cu-Ni-Co-O solid solution structure is formed, and compared with the intermittent doping of copper, the sensitivity of the detection on glucose can be obviously improved.
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 Cu-Ni-Co-O solid solution nano-fiber material has a three-dimensional porous net felt structure, and Cu ions are embedded into NiCo2O4Form a Cu-Ni-Co-O solid solution in the crystal lattice; the Cu-Ni-Co-O solid solution nanofiber material is characterized in that the molar ratio of Cu to Ni to Co to O in the Cu-Ni-Co-O solid solution nanofiber material is x (1-x) to 2:4, wherein x is 0.05-0.25; the Cu-Ni-Co-O solid solution nanofiber material is nanoscale in diameter and micron in length.
2. The Cu-Ni-Co-O solid solution nanofiber material as claimed in claim 1, wherein the diameter of the Cu-Ni-Co-O solid solution nanofiber material is 100 to 300 nm.
3. A method for preparing a Cu-Ni-Co-O solid solution nanofibrous material according to claim 1 or 2, characterised in that it comprises the following steps:
dissolving copper salt, nickel salt, cobalt salt and a template agent in a solvent to obtain spinning solution; the molar ratio of the copper in the copper salt to the nickel in the nickel salt to the cobalt in the cobalt salt is x (1-x) 2, wherein x is 0.05-0.25;
performing electrostatic spinning on the spinning solution to obtain metal salt/template agent composite nanofibers;
and calcining the metal salt/template agent composite nanofiber in an air atmosphere to obtain the Cu-Ni-Co-O solid solution nanofiber material.
4. The production method according to claim 3, wherein the template agent comprises polyvinylpyrrolidone, polyacrylonitrile or polyvinyl alcohol; the solvent comprises N, N-dimethylformamide, ethanol, chloroform or water; the ratio of the total mass of the copper salt, the nickel salt and the cobalt salt to the dosage of the solvent is (0.3-0.6) g (8-12) mL; the dosage ratio of the template agent to the solvent is (1.2-1.6) g:10 mL.
5. The production method according to claim 3, wherein the conditions for the electrospinning include: the spinning voltage is 7-20 kV, the receiving distance is 10-15 cm, and the diameter of the nozzle is 0.4-0.8 mm.
6. The preparation method according to claim 3, wherein the calcining temperature is 400-600 ℃ and the holding time is 0.5-2 h.
7. The Cu-Ni-Co-O solid solution nanofiber material as claimed in claim 1 or 2 or the Cu-Ni-Co-O solid solution nanofiber material prepared by the preparation method as claimed in any one of claims 3 to 6, and the application of the material in non-enzymatic electrochemical detection of glucose.
8. The application according to claim 7, characterized in that it is applied in such a way that: preparing the Cu-Ni-Co-O solid solution nanofiber material into a working electrode for detecting glucose;
the preparation method of the working electrode comprises the following steps:
dispersing the Cu-Ni-Co-O solid solution nano fiber material into a binder to obtain a Cu-Ni-Co-O solid solution nano fiber/binder suspension;
and coating the Cu-Ni-Co-O solid solution nanofiber/binder turbid liquid on the surface of a conductive current collector, calcining the conductive current collector coated with the turbid liquid, and removing the binder to obtain the working electrode.
9. Use according to claim 8, wherein the binder comprises triton, Nafion solution, conductive polymer PEDOT or PTFE; the dosage ratio of the Cu-Ni-Co-O solid solution nano-fiber material to the binder is (10-30) mg:0.1 mL.
10. The use according to claim 8, wherein the conductive current collector comprises ITO conductive glass, FTO conductive glass, stainless steel mesh, carbon cloth, copper foam or nickel foam; the calcining temperature is 350-450 ℃.
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