CN111359624B - Core-shell hollow Cu (OH) 2 @Au@Co(OH) 2 Composite material, preparation method and application - Google Patents
Core-shell hollow Cu (OH) 2 @Au@Co(OH) 2 Composite material, preparation method and application Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- 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
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- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- 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
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
Abstract
The invention discloses a core-shell hollow Cu (OH) 2 @Au@Co(OH) 2 Composite material, preparation method and application, wherein the microstructure of the product is controlled by adjusting the injection rate of the raw material liquid, and the synthesized precursor Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 The nano-gold particles have regular cubic morphology and are uniformly distributed at a core-shell interface, so that the conductivity of the material is obviously improved. Etching the precursor by NaOH with different concentrations to generate Cu (OH) 2 @Au@Co(OH) 2 The crystal has three-dimensional nanometer flower-like appearance, large specific surface area and many catalytic sites. Using Cu (OH) 2 @Au@Co(OH) 2 The electrochemical sensor prepared from the composite material is suitable for enzyme-free detection of glucose in serum, and has high sensitivity, strong stability and good selectivity.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to a core-shell hollow Cu (OH) 2 @Au@Co(OH) 2 Composite material, preparation method and application.
Background
According to the report of the world health organization, the number of diabetics is estimated to reach 5.78 hundred million by 2030. However, to date, no drug has been developed that can directly address the symptoms. If the blood sugar level cannot be controlled in time, diabetes can cause various feared complications such as renal failure, cataract, cerebral thrombosis and the like. Therefore, real-time monitoring of blood glucose levels is currently an effective prevention means. Among the glucose sensors of various types, electrochemical sensors have been the focus of research due to the characteristics of fast response speed, high sensitivity, simple operation, and easy miniaturization.
Electrochemical glucose sensors can be simply classified into enzyme sensing and non-enzyme sensing. Since the first enzyme electrode invented by Clark in 1962, enzyme sensing has rapidly developed and become commercially available through advantages in selectivity and specificity. However, because the enzyme is limited by protein, it is easily inactivated by the environmental influences of temperature, humidity, pH value and other toxic substances, and the accuracy is reduced. In addition, the enzyme protein synthesis process is complicated, the cost is high, and the defects of easy peeling from the surface of the electrode and the like exist. Therefore, enzyme sensing stability is general. The enzyme-free sensing is to utilize the self-catalytic property of the material to directly oxidize glucose electrically, thereby avoiding the limitation caused by the application of enzyme and having excellent stability and environmental applicability.
The catalytic material is the core of non-enzyme sensing and directly determines the level of an electrochemical signal. The key to realizing performance breakthrough of enzyme-free sensing is to prepare a sensing material with high catalytic activity. With the development of nanotechnology, the micro-morphology structure of the material is found to have a large influence on the self-catalytic activity. The purpose of achieving the performance improvement by regulating and controlling the nano structure of the material is a reliable method.
Disclosure of Invention
The invention aims to provide a core-shell hollow structure composite material Cu (OH) with a simple synthesis method 2 @Au@Co(OH) 2 The composite material can be used for preparing an electrochemical sensor for detecting enzyme-free glucose.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a core-shell hollow Cu (OH) 2 @Au@Co(OH) 2 The preparation method of the composite material comprises the following steps:
(1) Preparation of Au @ Co 2 [Fe(CN) 6 ] 3 : preparing K with the same concentration 3 Fe(CN) 6 And CoCl 2 The aqueous solution is combinedIs injected into a reaction vessel to generate Co 2 [Fe(CN) 6 ] 3 (ii) a Further preparing HAuCl 4 And C 6 H 8 O 6 Aqueous solution of HAuCl 4 Aqueous solution injection of Co 2 [Fe(CN) 6 ] 3 Stirring the solution for 10-60 min, adding C 6 H 8 O 6 For reducing HAuCl 4 Generation of Au @ Co 2 [Fe(CN) 6 ] 3 Centrifuging the solution, adding Au @ Co 2 [Fe(CN) 6 ] 3 Redispersion in water to give Au @ Co 2 [Fe(CN) 6 ] 3 An aqueous solution; in the process, after the reaction, other excessive reactants exist in the solution, which can influence the next step of coating the shell and needs to be removed, so the solution needs to be centrifuged to apply Au @ Co 2 [Fe(CN) 6 ] 3 Centrifuging the solution, and dissolving in fresh pure water;
(2) Preparation of Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 : preparing K with the same concentration 3 Fe(CN) 6 And CuCl 2 Aqueous solution and simultaneous injection into Au @ Co 2 [Fe(CN) 6 ] 3 Centrifuging the solution in an aqueous solution to remove Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 Dispersing in ethanol solution to obtain Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 Ethanol solution;
(3) Preparation of Cu (OH) 2 @Au@Co(OH) 2 : preparing strong alkaline aqueous solution and adding the strong alkaline aqueous solution to Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 In ethanol solution, centrifuging after ultrasonic homogenization and drying at room temperature to obtain Cu (OH) 2 @Au@Co(OH) 2 A composite material. The strong base aqueous solution is preferably an aqueous NaOH solution.
As a further improvement of the invention, K 3 Fe(CN) 6 The concentration of the aqueous solution of (A) is in the range of 1 to 100mM 2 The concentration of the aqueous solution is 1-100mM 2 The concentration of the aqueous solution is 1-100mM 4 The concentration of the aqueous solution is 0.5-10mM 6 H 8 O 6 The concentration range of the aqueous solution is 3.5-70mM, and the concentration range of the NaOH aqueous solution is 0.01-1M.
As a further improvement of the invention, K in step (1) 3 Fe(CN) 6 And CoCl 2 The volume ratio of (A) is 1-3:1-3, preferably 1:1; c 6 H 8 O 6 And HAuCl 4 The volume ratio of the aqueous solution is 5-10, preferably 7:1.
As a further improvement of the invention, K in step (2) 3 Fe(CN) 6 And CuCl 2 The volume ratio of the aqueous solution is 1-5:1-5, preferably 1:1.
As a further improvement of the invention, in the step (3), naOH aqueous solution and Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 The volume ratio of the ethanol solution is 1 to 3:1, preferably 2:1.
As a further improvement of the invention, K is injected in the step (1) 3 Fe(CN) 6 And CoCl 2 The volume of (a) is 5-80 mL; for redispersing Au @ Co 2 [Fe(CN) 6 ] 3 The volume of the water is 2-50 mL; step (2) injecting K 3 Fe(CN) 6 And CuCl 2 The volume of (A) is 5-80 mL; for redispersing Cu (OH) 2 @Au@Co(OH) 2 The volume of the ethanol is 2-50 mL; and (3) adding 10-100 mL of NaOH solution.
As a further improvement of the invention, K in step (1) 3 Fe(CN) 6 And CoCl 2 The injection rate of the reaction vessel is 500-1000 mu L/min, and as the process is an instant reaction, in order to control the appearance of the product, the invention utilizes the injection pump to adjust the reaction amount injected into the reaction vessel per minute to control the growth rate of the product crystal, thereby forming a regular appearance. The speed is too high, so that the phenomena of excessive crystal nuclei and agglomeration are easily caused; too slow a rate can cause a reaction time process and affect yield; HAuCl in step (1) 4 And C 6 H 8 O 6 The injection rate of (A) is 200-600 mu L/min, C 6 H 8 O 6 Is injected to reduce HAuCl 4 Formation of Au particles, control of C 6 H 8 O 6 The injection rate of (2) is to prevent the Au from being generated too fast and not being encapsulated in Co 2 [Fe(CN) 6 ] 3 Surface, but rather the problem of nucleation growth alone in solution; k in step (2) 3 Fe(CN) 6 And CuCl 2 The injection rate of (A) is 50-400 mu L/min, and the reaction of this step is to generate shell Co 2 [Fe(CN) 6 ] 3 Cu of core-shell structure 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 . The injection rate is too fast, and the generated Co 2 [Fe(CN) 6 ] 3 Can be independently nucleated in the solution to generate the self-polymerization phenomenon instead of being supported on Au @ Co 2 [Fe(CN) 6 ] 3 Growing on the particles.
As a further improvement of the invention, the centrifugation speed in the steps (1) to (3) is 2000r/min to 8000r/min, and the centrifugation time is 2min to 20min.
As a further improvement of the invention, the ultrasonic time in the step (3) is 5-30 min.
The invention also provides the core-shell hollow Cu (OH) prepared by the preparation method 2 @Au@Co(OH) 2 A composite material.
The invention also provides a method for preparing the core-shell hollow Cu (OH) 2 @Au@Co(OH) 2 An electrochemical sensor made of the composite material is used for detecting glucose without enzyme.
The preparation method of the electrochemical sensor comprises the step of preparing 2mg/mL Cu (OH) 2 @Au@Co(OH) 2 Taking 5 mu L of the aqueous solution, dripping the aqueous solution on a gold electrode, and drying the gold electrode at room temperature to obtain Cu (OH) 2 @Au@Co(OH) 2 An electrochemical sensor.
The invention discloses the following technical effects:
(1) The invention achieves the purpose of controlling the microstructure of the product by adjusting the injection rate of the raw material liquid, thereby improving the performance and synthesizing the precursor Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 The material has regular cubic morphology, and the nano gold particles are uniformly distributed at the core-shell interface, so that the contactable area is large, the conductivity of the material is obviously improved, the next step of etching with NaOH solution is facilitated, more catalytic sites are generated, the invention utilizes different NaOH concentrations to etch a precursor, and the generated Cu (OH) 2 @Au@Co(OH) 2 The crystal has three-dimensional nanometer flower-like appearance, large specific surface area and many catalytic sites.
(2) The nano gold particles are uniformly distributed in the middle of the core-shell interface, so that the conductivity of the material is obviously improved, and the electron transmission rate is accelerated.
(3) The core-shell structure has the advantages of stable structure, rich functions and the like, while the hollow structure has the advantages of large specific surface area, more active sites, short charge transmission path and the like. Therefore, combining these two morphologies is beneficial for the enhancement of electrical signals. Composite catalytic material Cu (OH) synthesized by the invention 2 @Au@Co(OH) 2 The catalyst has a core-shell hollow appearance, is stable in structure, large in specific surface area, multiple in catalytic sites, short in charge sensing path and very beneficial to enhancement of electrical signals.
(4) The preparation method of the invention is relatively convenient, has low cost, does not involve other irrelevant substances such as surfactant and the like, is beneficial to cleaning materials, and has very high application prospect.
(5) Based on Cu (OH) 2 @Au@Co(OH) 2 The modified sensor has high sensitivity (3587 muA. Multidot. MM) -1 ·cm -2 ) The stability is strong (the sensitivity still has 91.7 percent of the initial value after 30 days), the selectivity is good, and the glucose in serum can be accurately detected.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 shows Cu (OH) synthesized in example 1 2 @Au@Co(OH) 2 Electron micrographs of (A);
FIG. 2 shows Cu (OH) synthesized in example 1 2 @Au@Co(OH) 2 Transmission electron microscopy images of;
FIG. 3 shows Cu (OH) in use example 1 2 @Au@Co(OH) 2 Current-time plots of the prepared electrochemical sensor against glucose solution and rabbit serum;
FIG. 4 shows Cu (OH) synthesized in example 2 2 @Au@Co(OH) 2 Electron micrographs of (A);
FIG. 5 shows Cu (OH) synthesized in example 2 2 @Au@Co(OH) 2 Transmission electron microscopy images of;
FIG. 6 shows Cu (OH) in example 2 2 @Au@Co(OH) 2 Current-time plots of the prepared electrochemical sensor against glucose solution and rabbit serum;
FIG. 7 shows Cu (OH) synthesized in example 3 2 @Au@Co(OH) 2 Electron micrographs of (A);
FIG. 8 shows Cu (OH) synthesized in example 3 2 @Au@Co(OH) 2 Transmission electron microscopy images of;
FIG. 9 shows Cu (OH) in example 3 2 @Au@Co(OH) 2 Current-time plots of the prepared electrochemical sensors against glucose solution and rabbit serum.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) 20mM K was prepared 3 Fe(CN) 6 And 20mM CoCl 2 The aqueous solution was injected into the reaction vessel at a rate of 600. Mu.L/min simultaneously to form Co 2 [Fe(CN) 6 ] 3 (ii) a 1mM HAuCl was prepared 4 Aqueous solution and Co injection at 300. Mu.L/min 2 [Fe(CN) 6 ] 3 Stirring the solution for 30min; then 7mM C was prepared 6 H 8 O 6 Aqueous solution and reduced HAuCl was added at a rate of 500. Mu.L/min 4 Generation of Au @ Co 2 [Fe(CN) 6 ] 3 Centrifuging the solution at a centrifugation rate of 3000r/min for 10min and redispersing in a volume of 30mL of water;
(2) 20mM K was prepared 3 Fe(CN) 6 And 20mM CuCl 2 The aqueous solution is injected into Au @ Co at a rate of 300 μ L/min 2 [Fe(CN) 6 ] 3 In the aqueous solution, the solution was centrifuged at a centrifugation rate of 3000r/min for 10min and redispersed in 30mL of ethyl acetateIn an alcoholic solution;
(3) Preparing 0.4M NaOH aqueous solution, adding 20mL of NaOH aqueous solution into the ethanol solution, and obtaining Cu (OH) after ultrasonic treatment for 20min 2 @Au@Co(OH) 2 Centrifuging the solution at a centrifugation rate of 3000r/min and drying at room temperature;
(4) Taking 2mg/mL Cu (OH) 2 @Au@Co(OH) 2 Dripping 5 μ L of the aqueous solution on a gold electrode, and drying at room temperature to obtain Cu (OH) 2 @Au@Co(OH) 2 An electrochemical sensor.
Cu (OH) synthesized in this example 2 @Au@Co(OH) 2 FIG. 1 shows an electron micrograph of Cu (OH) synthesized in this example 2 @Au@Co(OH) 2 See fig. 2, and it can be seen from the chronoamperometric current test (fig. 3): the electrochemical sensor prepared in example 1 has an enzyme-free detection sensitivity of up to 3260. Mu.A. MM for glucose -1 ·cm -2 The detection limit was low, 0.5. Mu.M. The test result of the content of the glucose in the rabbit serum is 6.8mM, and the test result of the comparative commercial blood glucose sensor is 6.4mM, and the relative average standard deviation is calculated to be 7.5%, which shows that the electrochemical sensor prepared by the preparation method has higher accuracy in detecting the glucose in the serum.
Example 2
(1) Preparation of 5mM K 3 Fe(CN) 6 And 5mM CoCl 2 The aqueous solution was injected into the reaction vessel at a rate of 500. Mu.L/min simultaneously to form Co 2 [Fe(CN) 6 ] 3 (ii) a 5mM HAuCl was prepared 4 Aqueous solution and Co injection at a rate of 200. Mu.L/min 2 [Fe(CN) 6 ] 3 Stirring the solution for 30min; then 35mM C was prepared 6 H 8 O 6 Aqueous solution and reduced HAuCl was added at a rate of 400. Mu.L/min 4 Generation of Au @ Co 2 [Fe(CN) 6 ] 3 Centrifuging the solution at a centrifugation rate of 5000r/min for 15min and redispersing in 40mL volume of water;
(2) 5mM K was prepared 3 Fe(CN) 6 And 5mM CuCl 2 The aqueous solution was injected into Au @ Co at a rate of 200. Mu.L/min simultaneously 2 [Fe(CN) 6 ] 3 Centrifuging in water solution at a centrifugal rate of 5000r/minThe solution is 15min and dispersed in 40mL ethanol solution again;
(3) Preparing 0.8M NaOH aqueous solution, adding 30mL of NaOH aqueous solution into the ethanol solution, and carrying out ultrasonic treatment for 30min to obtain Cu (OH) 2 @Au@Co(OH) 2 Centrifuging the solution at a centrifugation rate of 5000r/min and drying at room temperature;
(4) Taking 2mg/mL Cu (OH) 2 @Au@Co(OH) 2 Dripping 5 μ L of the aqueous solution on a gold electrode, and drying at room temperature to obtain Cu (OH) 2 @Au@Co(OH) 2 An electrochemical sensor.
Cu (OH) synthesized in this example 2 @Au@Co(OH) 2 FIG. 4 shows an electron micrograph of Cu (OH) synthesized in this example 2 @Au@Co(OH) 2 See fig. 5, and it can be seen from the chronoamperometric current test (fig. 6): the electrochemical sensor prepared in example 2 has a detection sensitivity of up to 3347. Mu.A.mM for glucose in serum -1 ·cm -2 The detection limit was as low as 0.5. Mu.M. The result of the test on the glucose content in the rabbit serum is 5.5mM, and the result of the test on the comparative commercial blood glucose sensor is 5.2mM, and the relative average standard deviation is calculated to be 8.2%, which shows that the electrochemical sensor for detecting the glucose without the enzyme prepared by the preparation method has higher accuracy.
Example 3
(1) 40mM K was prepared 3 Fe(CN) 6 And 40mM CoCl 2 The aqueous solution was injected into the reaction vessel at a rate of 600. Mu.L/min simultaneously to form Co 2 [Fe(CN) 6 ] 3 (ii) a 1mM HAuCl was prepared 4 Aqueous solution and Co injection at 400. Mu.L/min 2 [Fe(CN) 6 ] 3 Stirring the solution for 30min; then 7mM C was prepared 6 H 8 O 6 Aqueous solution and reduced HAuCl was added at a rate of 500. Mu.L/min 4 Generation of Au @ Co 2 [Fe(CN) 6 ] 3 Centrifuging the solution at a centrifugation rate of 3000r/min for 10min and redispersing in a volume of 60mL water;
(2) 20mM K was prepared 3 Fe(CN) 6 And 20mM CuCl 2 The aqueous solution was injected into Au @ Co at a rate of 300. Mu.L/min simultaneously 2 [Fe(CN) 6 ] 3 In an aqueous solution at 3000r/min for 10min and redispersed in 30mL of ethanol solution;
(3) Preparing 0.4M NaOH aqueous solution, adding 40mL of NaOH aqueous solution into the ethanol solution, and performing ultrasonic treatment for 25min to obtain Cu (OH) 2 @Au@Co(OH) 2 Centrifuging the solution at a centrifugation rate of 3000r/min and drying at room temperature;
(4) Taking 2mg/mL Cu (OH) 2 @Au@Co(OH) 2 Dropping 5 μ L of the aqueous solution on a gold electrode, and drying at room temperature to obtain Cu (OH) 2 @Au@Co(OH) 2 An electrochemical sensor.
Cu (OH) synthesized in this example 2 @Au@Co(OH) 2 FIG. 7 shows an electron micrograph of Cu (OH) synthesized in this example 2 @Au@Co(OH) 2 See fig. 8, and it can be seen from the chronoamperometric current test (fig. 9): the electrochemical sensor prepared in example 3 has an enzyme-free detection sensitivity of up to 3169. Mu.A. MM for glucose -1 ·cm -2 The detection limit was low, 0.8. Mu.M. The test result of the content of the glucose in the rabbit serum is 4.6mM, and the test result of the comparative commercial blood glucose sensor is 4.1mM, and the relative average standard deviation is calculated to be 9.2%, which shows that the electrochemical sensor prepared by the preparation method has higher accuracy for detecting the glucose in the serum.
Example 4
(1) 60mM K was prepared 3 Fe(CN) 6 And 60mM CoCl 2 The aqueous solution was injected into the reaction vessel at a rate of 600. Mu.L/min simultaneously to form Co 2 [Fe(CN) 6 ] 3 (ii) a 7mM HAuCl was prepared 4 Aqueous solution and Co injection at a rate of 100. Mu.L/min 2 [Fe(CN) 6 ] 3 Stirring the solution for 30min; then 49mM C was prepared 6 H 8 O 6 Aqueous solution and reduced HAuCl was added at a rate of 200. Mu.L/min 4 Generation of Au @ Co 2 [Fe(CN) 6 ] 3 Centrifuging the solution at a centrifugation rate of 6000r/min for 20min and redispersing in a volume of 30mL of water;
(2) 20mM K was prepared 3 Fe(CN) 6 And 20mM CuCl 2 The aqueous solution was injected into Au @ Co at a rate of 300. Mu.L/min simultaneously 2 [Fe(CN) 6 ] 3 Centrifuging the solution in the water solution at a centrifugal rate of 5000r/min for 10min and dispersing the solution in 40mL of ethanol solution again;
(3) Preparing 0.8M NaOH aqueous solution, adding 80mL of NaOH aqueous solution into the ethanol solution, and performing ultrasonic treatment for 20min to obtain Cu (OH) 2 @Au@Co(OH) 2 Centrifuging the solution at a centrifugation rate of 4000r/min and drying at room temperature;
(4) Taking 2mg/mL Cu (OH) 2 @Au@Co(OH) 2 Dripping 5 μ L of the aqueous solution on a gold electrode, and drying at room temperature to obtain Cu (OH) 2 @Au@Co(OH) 2 An electrochemical sensor.
Through the timing ampere current test, the following results are obtained: the electrochemical sensor prepared in example 4 has a detection sensitivity of 3447. Mu.A.mM for glucose in serum -1 ·cm -2 The detection limit was as low as 0.4. Mu.M. The result of the test on the content of glucose in rabbit serum is 4.8mM, and the result of the test on the contrast commercial blood glucose sensor is 4.3mM, and the calculation of the relative average standard deviation is 5.2 percent, which indicates that the electrochemical sensor for detecting glucose without enzyme prepared by the preparation method has higher accuracy.
Example 5
(1) 80mM K was prepared 3 Fe(CN) 6 And 80mM CoCl 2 The aqueous solution was injected into the reaction vessel at a rate of 500. Mu.L/min simultaneously to form Co 2 [Fe(CN) 6 ] 3 (ii) a Preparation of 4mM HAuCl 4 Aqueous solution and Co injection at 400. Mu.L/min 2 [Fe(CN) 6 ] 3 Stirring the solution for 40min; then 16mM C was prepared 6 H 8 O 6 Aqueous solution and reduced HAuCl was added at a rate of 400. Mu.L/min 4 Generation of Au @ Co 2 [Fe(CN) 6 ] 3 Centrifuging the solution at a centrifugation rate of 6000r/min for 10min and redispersing in a volume of 20mL of water;
(2) 40mM K was prepared 3 Fe(CN) 6 And 40mM CuCl 2 The aqueous solution was injected into Au @ Co at a rate of 200. Mu.L/min simultaneously 2 [Fe(CN) 6 ] 3 In the water solution, the solution is centrifuged at the centrifugation speed of 6000r/min for 10min and is dispersed in 50mL ethanol solution again;
(3) Fitting for mixingPreparing 0.6M NaOH aqueous solution, adding 100mL of NaOH aqueous solution into the ethanol solution, and performing ultrasonic treatment for 30min to obtain Cu (OH) 2 @Au@Co(OH) 2 Centrifuging the solution at a centrifugation rate of 8000r/min and drying at room temperature;
(4) Taking 2mg/mL Cu (OH) 2 @Au@Co(OH) 2 Dripping 5 μ L of the aqueous solution on a gold electrode, and drying at room temperature to obtain Cu (OH) 2 @Au@Co(OH) 2 An electrochemical sensor.
Through the timing ampere current test, the following results are obtained: the electrochemical sensor prepared in example 5 has a detection sensitivity of 3147. Mu.A.mM for glucose in serum -1 ·cm -2 The detection limit was as low as 1. Mu.M. The result of the test on the glucose content in the rabbit serum is 5.8mM, and the result of the test on the comparative commercial blood glucose sensor is 5.2mM, and the relative average standard deviation is calculated to be 9.7%, which shows that the electrochemical sensor for detecting the glucose without the enzyme prepared by the preparation method has higher accuracy.
Example 6
(1) Preparation of 15mM K 3 Fe(CN) 6 And 15mM CoCl 2 The aqueous solution is injected into the reaction vessel at the same time at the rate of 800. Mu.L/min to generate Co 2 [Fe(CN) 6 ] 3 (ii) a Preparation of 3mM HAuCl 4 Aqueous solution and Co injection at a rate of 500. Mu.L/min 2 [Fe(CN) 6 ] 3 Stirring for 50min in the solution; then 6mM C was prepared 6 H 8 O 6 Aqueous solution and reduced HAuCl was added at a rate of 500. Mu.L/min 4 Generation of Au @ Co 2 [Fe(CN) 6 ] 3 Centrifuging the solution at a centrifugation rate of 8000r/min for 20min and redispersing in 30mL volumes of water;
(2) 10mM K was prepared 3 Fe(CN) 6 And 10mM CuCl 2 The aqueous solution was injected into Au @ Co at a rate of 200. Mu.L/min simultaneously 2 [Fe(CN) 6 ] 3 Centrifuging the solution in water solution at a centrifugation rate of 8000r/min for 5min and dispersing in 20mL ethanol solution again;
(3) Preparing 0.4M NaOH aqueous solution, adding 40mL of NaOH aqueous solution into the ethanol solution, and performing ultrasonic treatment for 10min to obtain Cu (OH) 2 @Au@Co(OH) 2 At a centrifugation rate of 6000r/minCentrifuging the solution and drying at room temperature;
(4) Taking 2mg/mL Cu (OH) 2 @Au@Co(OH) 2 Dripping 5 μ L of the aqueous solution on a gold electrode, and drying at room temperature to obtain Cu (OH) 2 @Au@Co(OH) 2 An electrochemical sensor.
The timing ampere current test shows that: the electrochemical sensor prepared in example 6 has a detection sensitivity of up to 3566. Mu.A.mM for glucose in serum -1 ·cm -2 The detection limit was as low as 0.4. Mu.M. The test result of the glucose content in the rabbit serum is 6.6mM, and the relative average standard deviation is calculated to be 3.2% compared with the test result of the commercial blood glucose sensor, which shows that the electrochemical sensor for detecting the glucose without the enzyme prepared by the preparation method has higher accuracy.
Comparative example 1
The only difference is K from example 1 3 Fe(CN) 6 And CoCl 2 The injection rate of (2) is 300. Mu.L/min; HAuCl in step (1) 4 And C 6 H 8 O 6 The injection rate of (A) is 50 μ L/min; k in step (2) 3 Fe(CN) 6 And CuCl 2 The injection rate of (2) was 10. Mu.L/min. Although the comparative example can form a regular core-shell structure, the comparative example takes too long time and has low productivity.
Comparative example 2
The only difference is K from example 1 3 Fe(CN) 6 And CoCl 2 The injection rate of (a) is 1300 μ L/min; HAuCl in step (1) 4 And C 6 H 8 O 6 The injection rate of (2) is 700. Mu.L/min; k in step (2) 3 Fe(CN) 6 And CuCl 2 The injection rate of (3) was 550. Mu.L/min. The particles formed by the comparative example do not form a core-shell structure, but are simply compounded, so that the performance is reduced.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. Core-shell hollow Cu (OH) 2 @Au@Co(OH) 2 The preparation method of the composite material is characterized by comprising the following steps:
(1) Preparation of Au @ Co 2 [Fe(CN) 6 ] 3 : preparing K with the same concentration 3 Fe(CN) 6 And CoCl 2 Simultaneously injecting the aqueous solution into the reaction vessel to generate Co 2 [Fe(CN) 6 ] 3 (ii) a Further preparing HAuCl 4 And C 6 H 8 O 6 Aqueous solution of HAuCl 4 Aqueous solution injection of Co 2 [Fe(CN) 6 ] 3 Stirring the solution, adding C 6 H 8 O 6 Generation of Au @ Co 2 [Fe(CN) 6 ] 3 Centrifuging the solution, adding Au @ Co 2 [Fe(CN) 6 ] 3 Redispersion in water to give Au @ Co 2 [Fe(CN) 6 ] 3 Aqueous solution, K 3 Fe(CN) 6 And CoCl 2 The injection rate of (A) is 500 to 1000 mu L/min; HAuCl 4 And C 6 H 8 O 6 The injection rate of (A) is 200 to 600 mu L/min;
(2) Preparation of Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 : preparing K with the same concentration 3 Fe(CN) 6 And CuCl 2 Aqueous solution and simultaneous injection into Au @ Co 2 [Fe(CN) 6 ] 3 In aqueous solution, K 3 Fe(CN) 6 And CuCl 2 The injection rate of (b) is 50 to 400 [ mu ] L/min, and the solution is centrifuged to produce Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 Mixing Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 Dispersing in ethanol solution to obtain Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 Ethanol solution;
(3) Preparation of Cu (OH) 2 @Au@Co(OH) 2 : preparing strong alkaline aqueous solution and adding the strong alkaline aqueous solution to Cu 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 In ethanol solution, centrifuging after ultrasonic homogenization and drying at room temperature to obtain Cu (OH) 2 @Au@Co(OH) 2 A composite material.
2. The method of claim 1, wherein K is 3 Fe(CN) 6 The concentration of the aqueous solution of (1) to 100mM 2 The concentration of the aqueous solution is 1 to 100mM 2 The concentration of the aqueous solution is 1 to 100mM 4 The concentration range of the aqueous solution is 0.5 to 10mM 6 H 8 O 6 The concentration range of the aqueous solution is 3.5 to 70mM, and the concentration range of the strong alkali aqueous solution is 0.01 to 1M.
3. The method according to claim 1, wherein K is in step (1) 3 Fe(CN) 6 And CoCl 2 The volume ratio of (A) is 1-3:1-3; c 6 H 8 O 6 And HAuCl 4 The volume ratio of the aqueous solution is 5-10.
4. The method according to claim 1, wherein K is in step (2) 3 Fe(CN) 6 And CuCl 2 The volume ratio of the aqueous solution is 1-5:1-5.
5. The method according to claim 1, wherein the strongly alkaline aqueous solution and Cu are used in the step (3) 2 [Fe(CN) 6 ] 3 @Au@Co 2 [Fe(CN) 6 ] 3 The volume ratio of the ethanol solution is 1-3:1.
6. The preparation method according to claim 1, wherein the centrifugation speed in steps (1) to (3) is 2000r/min to 8000r/min, and the centrifugation time is 2min to 20min.
7. The method according to claim 1, wherein the ultrasonic treatment in step (3) is carried out for 5 to 30min.
8. Core-shell hollow Cu (OH) 2 @Au@Co(OH) 2 Composite material, characterized in that it is prepared according to the preparation method of any one of claims 1~7.
9. The core-shell hollow Cu (OH) of claim 8 2 @Au@Co(OH) 2 An electrochemical sensor prepared from the composite material is characterized in that the electrochemical sensor is used for detecting glucose without enzyme.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100375A (en) * | 2013-01-17 | 2013-05-15 | 浙江大学 | Preparation method and application of porous gelatin protein composite thin film modified by ferrous cyanide ions |
| CN103193276A (en) * | 2013-04-28 | 2013-07-10 | 北京化工大学 | Method for synthesizing iron-containing hydrotalcite-like compound by utilizing prussian blue as raw material |
| CN104865298A (en) * | 2015-03-26 | 2015-08-26 | 桂林电子科技大学 | Preparation method and applications of polypyrrole-graphene-Prussian Blue nanometer composite material |
| CN106290517A (en) * | 2016-08-15 | 2017-01-04 | 中驭(北京)生物工程有限公司 | A kind of highly sensitive glucose is without enzyme sensor electrode material and preparation method thereof |
| CN107234238A (en) * | 2017-05-03 | 2017-10-10 | 太原理工大学 | A kind of core shell structure Au@Co (OH)2The preparation method of nanoparticle |
| CN109267117A (en) * | 2018-09-27 | 2019-01-25 | 安庆北化大科技园有限公司 | A kind of electrode material and preparation method thereof of multi-stage nano composite construction |
| CN109592721A (en) * | 2019-01-21 | 2019-04-09 | 北京航空航天大学 | A kind of porous Ni (OH)2Nanocages and preparation method thereof |
| CN109778172A (en) * | 2019-02-21 | 2019-05-21 | 东华大学 | One kind is for non-enzymatic glucose sensor composite nano materials and preparation method thereof |
| CN110818031A (en) * | 2019-10-31 | 2020-02-21 | 燕山大学 | Preparation method of composite metal oxide functional electrode |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060177660A1 (en) * | 2005-02-09 | 2006-08-10 | Challa Kumar | Core-shell nanostructures and microstructures |
-
2020
- 2020-04-21 CN CN202010315134.8A patent/CN111359624B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100375A (en) * | 2013-01-17 | 2013-05-15 | 浙江大学 | Preparation method and application of porous gelatin protein composite thin film modified by ferrous cyanide ions |
| CN103193276A (en) * | 2013-04-28 | 2013-07-10 | 北京化工大学 | Method for synthesizing iron-containing hydrotalcite-like compound by utilizing prussian blue as raw material |
| CN104865298A (en) * | 2015-03-26 | 2015-08-26 | 桂林电子科技大学 | Preparation method and applications of polypyrrole-graphene-Prussian Blue nanometer composite material |
| CN106290517A (en) * | 2016-08-15 | 2017-01-04 | 中驭(北京)生物工程有限公司 | A kind of highly sensitive glucose is without enzyme sensor electrode material and preparation method thereof |
| CN107234238A (en) * | 2017-05-03 | 2017-10-10 | 太原理工大学 | A kind of core shell structure Au@Co (OH)2The preparation method of nanoparticle |
| CN109267117A (en) * | 2018-09-27 | 2019-01-25 | 安庆北化大科技园有限公司 | A kind of electrode material and preparation method thereof of multi-stage nano composite construction |
| CN109592721A (en) * | 2019-01-21 | 2019-04-09 | 北京航空航天大学 | A kind of porous Ni (OH)2Nanocages and preparation method thereof |
| CN109778172A (en) * | 2019-02-21 | 2019-05-21 | 东华大学 | One kind is for non-enzymatic glucose sensor composite nano materials and preparation method thereof |
| CN110818031A (en) * | 2019-10-31 | 2020-02-21 | 燕山大学 | Preparation method of composite metal oxide functional electrode |
Non-Patent Citations (2)
| Title |
|---|
| Simultaneous biosensing of catechol and hydroquinone via a truncated cubeshaped Au/PBA nanocomposite;Danfeng Jiang et al.;《Biosensors and Bioelectronics》;20190115;第124卷;第260-267页 * |
| Wet chemical synthesis and magnetic properties of core–shell nanocolumns of Ni(OH)2@Co(OH)2 and their oxides;Meng Yao et al.;《CrystEngComm》;20110210;第13卷;第2593–2598页 * |
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