CN112899820B - Cu-Ni-Co-O solid solution nanofiber material and preparation method and application thereof - Google Patents
Cu-Ni-Co-O solid solution nanofiber 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 glucose sensor using the conventional biological enzyme method has excellent selectivity due to the use of glucose oxidase or glucose dehydrogenase. However, enzyme-based sensors involve complex 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.
Currently, 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, NiCo 2 O 4 The prepared electrode material has excellent electrocatalytic performance, high sensitivity and stability, and is an excellent electrode material for the electrocatalytic oxidation of glucose. To further improve NiCo 2 O 4 In the above, researchers have attempted to improve the electrocatalytic 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 method 2 O 4 Hollow nanorods and their use in electrochemical glucose sensing [ Yang J, Cho M, Lee Y. Synthesis of chromatographic NiCo 2 O 4 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 structure 2 O 4 @ polyaniline (NiCo) 2 O 4 @ PANI) nanocomposite and its use in electrochemical glucose detection [ Zhiyuan, Yu, Hejun, et al 2 O 4 @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 assay 2 O 4 Nano-needle modified electrospun carbon nano-composite fiber membrane and its use in electrochemical glucose detection [ Liu L, Wang Z, Yang J, et al 2 O 4 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) have low sensitivity to glucose; NiCo obtained by the method of (3) 2 O 4 Although the sensitivity of the nanoneedle array to glucose is improved, 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 as well as 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, wherein Cu ions are embedded into NiCo 2 O 4 Form 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 a 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 the 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, wherein Cu ions are embedded into NiCo 2 O 4 A Cu-Ni-Co-O solid solution is formed in the crystal lattice of (1). On one hand, the Cu-Ni-Co-O solid solution has a three-dimensional porous net felt structure, can adsorb more glucose molecules, and simultaneously has an ultra-long one-dimensional nanofiber structure, so that an ion transmission path can be shortened, electrons can be conveniently and quickly 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+ 、Ni 2+ 、Co 3+ ) And more variable price conversion
Is easy to generate with glucose under electrochemical environmentAnd oxidation-reduction reaction is carried out, so that the sensitivity of the glucose detection is improved.
Compared with copper ion interstitial doped NiCo 2 O 4 The doping amount of copper ions is limited (within 10%), and the invention embeds the copper ions into NiCo 2 O 4 The content of copper is favorably improved in the interior of 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 invention 0.05 Ni 0.95 Co 2 O 4 Scanning electron microscope photographs of the solid solution nanofiber material;
FIG. 2 shows Cu prepared in example 2 of the present invention 0.15 Ni 0.85 Co 2 O 4 Scanning electron micrographs of solid solution nanofiber materials;
FIG. 3 shows Cu prepared in example 3 of the present invention 0.25 Ni 0.75 Co 2 O 4 Scanning 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 invention 2 O 4 Scanning electron micrographs of nanofiber materials;
FIG. 5 is a graph of CuCo prepared in comparative example 2 of the present invention 2 O 4 Scanning electron microscope photos of the nanofiber material;
FIG. 6 is a 10% Cu-NiCo sample prepared according to comparative example 3 of the present invention 2 O 4 Scanning electron microscope photographs 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 Cu 0.05 Ni 0.95 Co 2 O 4 A solid solution nanofiber material, B is Cu 0.15 Ni 0.85 Co 2 O 4 A solid solution nanofiber material, C being Cu 0.25 Ni 0.75 Co 2 O 4 A solid solution nanofiber material, D is NiCo 2 O 4 Nanofibers, E is CuCo 2 O 4 Nanofibers, F is 10% Cu-NiCo 2 O 4 A nanofiber;
FIG. 8 is a Cu film prepared in comparative example 4 of the present invention 0.35 Ni 0.65 Co 2 O 4 An X-ray diffraction spectrum of the nanofiber material;
FIG. 9 shows Cu prepared in example 3 of the present invention 0.25 Ni 0.75 Co 2 O 4 High resolution transmission electron microscopy of solid solution nanofiber materials;
FIG. 10 shows Cu prepared in example 3 of the present invention 0.25 Ni 0.75 Co 2 O 4 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, wherein Cu ions are embedded into NiCo 2 O 4 A Cu-Ni-Co-O solid solution is formed in the crystal lattice of (1).
In the Cu-Ni-Co-O solid solution nanofiber material, the molar ratio of Cu, Ni, Co and O in the Cu-Ni-Co-O solid solution nanofiber material is x (1-x):2:4, wherein x is 0.05-0.25, and is preferably 0.25. The invention embeds copper ions into NiCo 2 O 4 The content of copper is favorably improved in the interior of 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 in a nanometer 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+ 、Ni 2+ 、Co 3+ ) 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.
The invention provides a preparation method of the Cu-Ni-Co-O solid solution nanofiber material, which comprises the following steps:
dissolving copper salt, nickel salt, cobalt salt and a template agent in a solvent to obtain a 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 the 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 invention, a proper solvent is preferably selected according to the type of the template, and the solvent can be used for completely dissolving the copper salt, the nickel salt, the cobalt salt and the template. 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 dosage of the solvent is preferably (0.3-0.6) g and (8-12) mL, and more preferably (0.3-0.6) g and 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 above 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 calcining temperature is preferably 400-600 ℃, more preferably 450-550 ℃, and most preferably 500 ℃; the heat preservation time of the calcination 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 within 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 oversize 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 preparation method in 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 comprises the steps of:
dispersing the Cu-Ni-Co-O solid solution nanofiber material into a binder to obtain a Cu-Ni-Co-O solid solution nanofiber/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 requirements on the specific type of the binder, and the binder can be specifically but 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 0.25cm 2 The 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, preventing the electrode material from falling off during testing in the 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 in detail herein.
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 filled in a medical syringe having a nozzle with a diameter of 0.4mm, the distance between the nozzle and the grounded receiving plate was maintained at 15cm, a gold electrode was put in the solution and applied with a high voltage of 7kV to perform electrostatic spinning, and a metal salt/templating agent composite nanofiber was prepared. Finally, the metal salt/template composite nano-fiber is calcined for 2 hours in a muffle furnace at a high temperature of 500 ℃ at a speed of 2 ℃/min to obtain Cu 0.05 Ni 0.95 Co 2 O 4 A solid solution nanofiber material.
Produced Cu 0.05 Ni 0.95 Co 2 O 4 Scanning electron micrograph of the solid solution nanofibers is shown in FIG. 1, from which it is clear that Cu was produced 0.05 Ni 0.95 Co 2 O 4 The solid solution nanofiber is a three-dimensional porous net felt structure with the diameter of about 100-300 nm.
The obtained Cu 0.05 Ni 0.95 Co 2 O 4 The X-ray diffraction pattern analysis of the solid solution nano-fiber is carried out, the result is shown as the curve A in figure 7, the X-ray diffraction pattern and NiCo thereof 2 O 4 The characteristic diffraction peak is completely consistent, and the characteristic diffraction peak related to Cu is not observed, which indicates that the spinel structure of the prepared nanofiber material is not changed, and proves that the Cu is successfully prepared 0.05 Ni 0.95 Co 2 O 4 A solid solution material.
20mg of Cu obtained in this example 0.05 Ni 0.95 Co 2 O 4 Adding the solid solution nanofiber material into 0.1mL of triton, and carrying out ultrasonic treatment for 1min to obtain Cu 0.05 Ni 0.95 Co 2 O 4 Solid solution nanofiber/triton suspension. Taking 30 mu L of Cu 0.05 Ni 0.95 Co 2 O 4 And (3) coating the solid solution nanofiber/triton suspension on the surface of 1cm multiplied by 2cm 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 suspension-coated ITO conductive glass for 2 hours at high temperature, and removing 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. The glucose concentration is measured by adopting an amperometric amperometry (I-T), the working voltage is 0.55V, 20mL of 0.1mol/L sodium hydroxide solution is added into a beaker to be used as electrolyte, different amounts of glucose are added at certain intervals, and the adding steps are as follows: the interval time of dripping glucose every time is 50 s; first, 10. mu.L of a 0.1M glucose solution (the glucose concentration in the solution increases by 0.05mM after each addition) and 20. mu.L of a 0.1M glucose solution (the glucose concentration in the solution increases 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 four times 5. mu.L of 1M glucose solution (glucose concentration in the solution increased by 0.25mM after each addition) and finally eight times 10. mu.L of 1M glucose solution (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. multidot.mM when the glucose concentration is 2-6 mM -1 ·cm -2 。
Example 2
The difference from the embodiment 1 lies inAdding 0.075mmol and 0.425mmol of copper acetate monohydrate and nickel acetate tetrahydrate respectively, wherein the corresponding molar ratio of copper, nickel and cobalt is 0.15:0.85:2, and preparing Cu 0.15 Ni 0.85 Co 2 O 4 A solid solution nanofiber material.
Produced Cu 0.15 Ni 0.85 Co 2 O 4 Scanning electron micrograph of solid solution nanofibers is shown in FIG. 2, from which the Cu produced is clearly visible 0.15 Ni 0.85 Co 2 O 4 The solid solution nanofiber is a three-dimensional porous net felt structure with the diameter of about 100-200 nm.
The obtained Cu 0.15 Ni 0.85 Co 2 O 4 The 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 thereof 2 O 4 The 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 prepared 0.15 Ni 0.85 Co 2 O 4 A solid solution material.
Example 3
The difference from example 1 is that copper acetate monohydrate and nickel acetate tetrahydrate are 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 Cu 0.25 Ni 0.75 Co 2 O 4 A solid solution nanofiber material.
Produced Cu 0.25 Ni 0.75 Co 2 O 4 Scanning electron micrograph of solid solution nanofibers is shown in FIG. 3, from which the Cu produced is clearly visible 0.25 Ni 0.75 Co 2 O 4 The solid solution nanofiber is a three-dimensional porous net felt structure with the diameter of about 100-200 nm.
The obtained Cu 0.25 Ni 0.75 Co 2 O 4 The 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 in 2 O 4 Characteristic diffraction peak ofThe method is completely consistent, and no characteristic diffraction peak related to Cu is observed, so that the spinel structure of the prepared nanofiber material is not changed, and the successful preparation of Cu is proved 0.25 Ni 0.75 Co 2 O 4 A solid solution material.
FIG. 9 shows Cu prepared in this example 0.25 Ni 0.75 Co 2 O 4 High resolution TEM image of solid solution nanofiber material, from which a lattice spacing of 0.204nm, corresponding to NiCo, can be clearly observed 2 O 4 The (400) crystal face of the crystal is consistent with the result of an X-ray diffraction pattern.
Cu obtained in this example was treated by the method of example 1 0.25 Ni 0.75 Co 2 O 4 The 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 obtained 2 O 4 And (3) nano fibers.
The NiCo is prepared 2 O 4 The scanning electron micrograph of the nanofibers is shown in FIG. 4, from which it is clear that NiCo was produced 2 O 4 The nanofiber is of a three-dimensional porous net felt structure with the diameter of about 100-300 nm.
The NiCo prepared is 2 O 4 The 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 are 2 O 4 The characteristic diffraction peaks of the crystal are completely consistent, which proves that the NiCo with the spinel structure is successfully prepared 2 O 4 A 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 CuCo 2 O 4 And (3) nano fibers.
The obtained CuCo 2 O 4 The scanning electron micrograph of the nanofibers is shown in FIG. 5, from which the CuCo produced is clearly seen 2 O 4 The nano-fiber is a three-dimensional porous net felt structure with the diameter of about 100-300 nm.
The prepared CuCo 2 O 4 The X-ray diffraction pattern of the nanofiber is analyzed, and the result is shown as the curve E in figure 7, and the X-ray diffraction pattern and the CuCo 2 O 4 The characteristic diffraction peaks are completely consistent, and the successful preparation of the CuCo with the spinel structure is proved 2 O 4 A material.
Comparative example 3
The difference from example 1 is that copper acetate monohydrate and nickel acetate tetrahydrate are added in amounts of 0.05mmol and 0.5mmol, respectively, corresponding to a molar ratio of copper, nickel and cobalt of 0.1:1:2, to obtain 10% copper interstitial doped NiCo 2 O 4 Nanofibers, 10% Cu-NiCo 2 O 4 And (3) nano fibers.
The 10% Cu-NiCo is obtained 2 O 4 Scanning electron micrograph of the nanofibers is shown in FIG. 6, from which it is clear that 10% Cu-NiCo was produced 2 O 4 The nano-fiber is a three-dimensional porous net felt structure with the diameter of about 100-300 nm.
The prepared 10% Cu-NiCo 2 O 4 The 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 are 2 O 4 Substantially identical.
Comparative example 4
The difference from example 1 is that copper acetate monohydrate and nickel acetate tetrahydrate are 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 Cu 0.35 Ni 0.65 Co 2 O 4 A nanofiber material.
The obtained Cu 0.35 Ni 0.65 Co 2 O 4 The 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 NiCo 2 O 4 In 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 method of reference example 1 was used to detect glucose using the nanofibers of examples 2-3 and comparative examples 1-4, respectively, 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 apparent from the results of Table 1, the present invention is achieved by introducing Cu into NiCo 2 O 4 In addition, a Cu-Ni-Co-O solid solution structure can be formed by controlling the doping amount of Cu, and compared with the intermittent doping of copper, the sensitivity of the detection of 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 amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered 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 NiCo 2 O 4 Form 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 Cu-Ni-Co-O solid solution nanofiber material has a diameter of 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 a 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 the 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 method of claim 3, wherein 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.
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 nanofiber material into a binder to obtain a Cu-Ni-Co-O solid solution nanofiber/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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